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WO2019009365A1 - Temporary adhesive agent containing phenyl-group-containing polysiloxane - Google Patents

Temporary adhesive agent containing phenyl-group-containing polysiloxane Download PDF

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Publication number
WO2019009365A1
WO2019009365A1 PCT/JP2018/025542 JP2018025542W WO2019009365A1 WO 2019009365 A1 WO2019009365 A1 WO 2019009365A1 JP 2018025542 W JP2018025542 W JP 2018025542W WO 2019009365 A1 WO2019009365 A1 WO 2019009365A1
Authority
WO
WIPO (PCT)
Prior art keywords
wafer
substrate
adhesive
component
group
Prior art date
Application number
PCT/JP2018/025542
Other languages
French (fr)
Japanese (ja)
Inventor
俊介 森谷
榎本　智之
徹也 新城
浩司 荻野
和宏 澤田
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to SG11202000059QA priority Critical patent/SG11202000059QA/en
Priority to US16/627,993 priority patent/US11345837B2/en
Priority to EP18828060.6A priority patent/EP3651186A4/en
Priority to KR1020207001260A priority patent/KR102520889B1/en
Priority to JP2019527965A priority patent/JP7168916B2/en
Priority to CN201880045131.8A priority patent/CN110870049B/en
Publication of WO2019009365A1 publication Critical patent/WO2019009365A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer

Definitions

  • the present invention relates to a temporary adhesive for fixing a wafer to a support during polishing of the back surface of the wafer and a laminate using the same.
  • each wafer to be integrated is thinned by polishing on the side opposite to the formed circuit surface (i.e., the back surface), and the thinned semiconductor wafers are stacked.
  • a semiconductor wafer (also referred to herein as just a wafer) before thinning is bonded to a support for polishing in a polishing apparatus.
  • the adhesion at that time is called temporary adhesion because the semiconductor wafer must be easily peeled off after polishing. This temporary bond must be easily removed from the support, and if a large force is applied for removal, the thinned semiconductor wafer may be cut or deformed, which does not occur. As well, easily removed. However, it is also not preferable that the semiconductor wafer is dislodged or deviated by polishing stress at the time of back surface polishing. Therefore, the performance required for temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.
  • Patent Document 1 and Patent Document 2 a method having an adhesion layer and a separation layer, wherein the separation layer is formed by plasma polymerization of dimethylsiloxane and mechanically separated after polishing
  • Patent Document 3 A method of bonding a support substrate and a semiconductor wafer with an adhesive composition, polishing the back surface of the semiconductor wafer and then removing the adhesive with an etching solution
  • Patent Document 3 A processed wafer comprising a combination of a polymerization layer obtained by polymerizing an alkenyl group-containing organopolysiloxane and a hydrosilyl group-containing organopolysiloxane with a platinum catalyst and a polymerization layer formed of a thermosetting polysiloxane
  • Patent Document 4 Patent Reference 5 and Patent Document 6 and Patent Document 7 are disclosed.
  • the present invention is, as a first aspect, an adhesive for releasably bonding between a support and a circuit surface of a wafer and processing the back surface of the wafer, wherein the adhesive cures by a hydrosilylation reaction ((1) The adhesive containing A) and a component (B) containing a phenyl group-containing polyorganosiloxane, wherein the weight percentage of the component (A) and the component (B) is a ratio of 95: 5 to 30:70,
  • component (A) siloxane units (Q units) represented by SiO 2, siloxane units (M units) represented by R 1 R 2 R 3 SiO 1/2 , R 4 R 5 SiO
  • the monovalent chemical group represented by R 1 to R 6 is an alkyl group having 1 to 10 carbon atoms and the number of carbon atoms, each of which is a C bond or a Si—H bond.
  • the adhesive according to the first aspect which comprises a polysiloxane (A1) containing the above, and a platinum group metal-based catalyst (A2),
  • the adhesive according to any one of the first to third aspects, wherein the processing is polishing the back surface of a wafer
  • the adhesive according to any one of the first to fourth aspects is applied onto a first substrate to form an adhesive layer, and a second substrate is joined and heated from the first substrate side Bonding method of laminates,
  • the bonding method according to the fifth aspect wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  • the bonding method according to the fifth aspect wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
  • the adhesive according to any one of the first to third aspects is coated on a first substrate to form an adhesive layer, a second substrate is joined, and heating is performed from the first substrate side. After curing the adhesive to form a laminate, the laminate is processed, and a peeling method which causes peeling between the first substrate, the second substrate and the adhesive layer,
  • the adhesive described in the fourth aspect is coated on the first substrate to form an adhesive layer, the second substrate is joined, and the adhesive is cured by heating from the first substrate side to form a laminate. And processing the laminate to form a peeling between the first substrate, the second substrate and the adhesive layer,
  • the peeling method according to the eighth aspect wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate,
  • the peeling method according to the ninth aspect wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate,
  • the peeling method according to the eighth aspect wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
  • the peeling method according to the ninth aspect wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
  • the processing is polishing the back surface of the wafer.
  • the component (A) is an adhesive for releasably bonding between a support and a circuit surface of a wafer to process the back surface of the wafer, and curing by a hydrosilylation reaction
  • An adhesive (temporary adhesive) characterized by including a phenyl group-containing polyorganosiloxane component (B) is provided.
  • the temporary adhesive loaded between the support and the circuit surface of the wafer includes a component (A) that crosslinks and hardens by a hydrosilylation reaction, and a component (B) having a phenyl group; It is a laminate for processing the back side of the wafer on the opposite side, and by combining polysiloxane of a specific component, it excels in spin coatability to the circuit side of the wafer, and when bonding with adhesive layer or processing the back side of wafer It is possible to easily peel off after processing the back surface of the wafer, that is, after polishing, and after peeling off, the adhesive agent attached to the wafer or the support can be easily removed by a solvent or a tape.
  • the processing on the opposite side of the circuit surface of the wafer involves thinning of the wafer by polishing. Thereafter, through silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a laminated body of wafers, which is three-dimensionally mounted. In addition, the formation of a wafer back surface electrode and the like is also performed before and after that. While wafer thinning and TSV processes are subjected to heat at 250-350 ° C while bonded to a support, laminates as adhesives used in the present invention have their heat resistance .
  • the present invention is an adhesive for releasably bonding between a support and a circuit surface of a wafer and processing the back surface of the wafer, wherein the adhesive cures by a hydrosilylation reaction and contains a component (A) and a phenyl group.
  • the adhesive which comprises a component (B) containing a polyorganosiloxane and the ratio by mass of the component (A) to the component (B) is 95: 5 to 30:70.
  • the thickness of the wafer can be reduced by temporarily bonding the support and the wafer with an adhesive and processing the back surface of the wafer opposite to the circuit surface by polishing or the like.
  • the temporary adhesion is performed when the back of the wafer is polished, and after the back of the wafer is polished, the support and the thinned wafer can be separated.
  • peelable means that the peel strength is lower than at other peel points, and it is easy to peel.
  • the adhesive layer is formed by an adhesive.
  • the adhesive contains the component (A) and the component (B), and may further contain other additives.
  • Component (A) is a siloxane unit represented by SiO 2 (Q unit), a siloxane unit represented by R 1 R 2 R 3 SiO 1/2 (M unit), R 4 R 5 SiO 2/2 Selected from the group consisting of the siloxane unit (D unit) and the siloxane unit (T unit) represented by R 6 SiO 3/2 (wherein R 1 to R 6 each represent a Si—C bond or Si— And the monovalent chemical group represented by R 1 to R 6 is an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms.
  • a polysiloxane comprising a polyorganosiloxane (a1) containing a group and a polyorganosiloxane (a2) wherein the monovalent chemical group represented by R 1 to R 6 contains an alkyl group having 1 to 10 carbon atoms and a hydrogen atom, respectively It contains a xanthan (A1) and a platinum group metal-based catalyst (A2).
  • Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2).
  • the polyorganosiloxane (a1) contains an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms
  • the polyorganosiloxane (a2) has an alkyl group having 1 to 10 carbon atoms and a hydrogen atom Contains.
  • the alkenyl group and the Si-H group form a crosslinked structure by the hydrosilylation reaction with the platinum group metal catalyst (A2) and cure.
  • the polyorganosiloxane (a1) is selected from Q unit, M unit, D unit and T unit, for example, a combination of (Q unit and M unit) and (D unit and M unit), (T unit and M unit) Combination of (D unit and M unit), combination of (Q unit, T unit and M unit) and (T unit and M unit), combination of (T unit and M unit), (Q unit and M unit) Can be formed by a combination of
  • the polyorganosiloxane (a2) is selected from Q unit, M unit, D unit, T unit, for example, a combination of (M unit and D unit), a combination of (Q unit and M unit), (Q unit and T unit) And M units) can be formed.
  • the alkenyl group having 2 to 10 carbon atoms is, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-Methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group , 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl -2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-
  • the alkyl group having 1 to 10 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-butyl group Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl- n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-di
  • the polyorganosiloxane (a1) is composed of an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms is a methyl group and has 2 to 6 carbon atoms
  • the alkenyl group of 10 is an ethenyl group, that is, a vinyl group, and 0.1% by mole to 50.0% by mole, preferably 0.5% by mole, of all substituents represented by R 1 to R 6 in which the alkenyl group is represented by R 1 to R 6 It can be 30.0 mol%, and the remaining R 1 to R 6 can be alkyl groups.
  • the polyorganosiloxane (a2) is composed of an alkyl group having 1 to 10 carbon atoms and a hydrogen atom, the alkyl group having 1 to 10 carbon atoms is a methyl group, and the hydrogen atom forms a structure of Si-H Do.
  • Hydrogen atom that is, 0.1 to 50.0 mol%, preferably 10.0 to 40.0 mol%, in all substituents represented by R 1 to R 6 in a hydrogen atom;
  • the remaining R 1 to R 6 can be alkyl groups.
  • the molar ratio of hydrogen atoms represented by the alkenyl group and the Si-H group is in the range of 2.0: 1.0, preferably 1.5: 1.0. Can be contained in
  • the polyorganosiloxane (a1) and the polyorganosiloxane (a2) can be used in a weight average molecular weight of 500 to 1,000,000, or 5,000 to 50,000, respectively.
  • Component (A) contains a platinum group metal catalyst (A2).
  • a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation addition reaction of an alkenyl group and a Si-H group, and is a reaction of platinum black, platinum chloride, platinum chloride acid, chloride acid and alcohol and monohydric alcohol.
  • Platinum-based catalysts such as complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate are used. Examples of complexes of platinum and olefins include complexes of divinyl tetramethyldisiloxane and platinum.
  • the addition amount of the platinum catalyst can be added in the range of 1.0 to 50.0 ppm with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
  • Component (A) can further add an alkynyl alcohol as an inhibitor (A3) to suppress the progress of the hydrosilylation reaction.
  • an alkynyl alcohol as an inhibitor (A3) to suppress the progress of the hydrosilylation reaction.
  • the inhibitor include 1-ethynyl-1-cyclohexanol and the like. These inhibitors can be added in the range of 1000.0 to 10000.0 ppm with respect to the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
  • the polyorganosiloxane used for the component (B) of this invention can use the combination of (b1) phenyl methyl siloxane unit structure or diphenyl siloxane unit structure, and (b2) dimethylsiloxane unit structure.
  • the above (b1) contains a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 (wherein R 1 and R 2 are each bonded to a silicon atom by a Si—C bond), 1 is a phenyl group or an alkyl group having 1 to 10 carbon atoms (particularly preferably a methyl group), and R 2 is a phenyl group.
  • D unit siloxane unit
  • the above (b2) contains a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 (wherein R 1 and R 2 are each bonded to a silicon atom by a Si—C bond), 1 and R 2 each represent an alkyl group having 1 to 10 carbon atoms (in particular, a methyl group is preferable).
  • D unit siloxane unit represented by R 1 R 2 SiO 2/2 (wherein R 1 and R 2 are each bonded to a silicon atom by a Si—C bond), 1 and R 2 each represent an alkyl group having 1 to 10 carbon atoms (in particular, a methyl group is preferable).
  • the alkyl group is preferably a methyl group, and the phenyl group has a structure bonded to a silicon atom via a linking group or directly.
  • the polyorganosiloxane used for the component (B) contains siloxane units (D units), but may contain Q units, M units and T units.
  • D units siloxane units
  • Q units Q units
  • M units and T units a combination of D units, Q units and M units
  • D unit, M unit and T unit a combination of D units, Q units and M units
  • D unit, M unit and T unit the combination of D unit, Q unit, M unit and T unit, etc. may be mentioned.
  • the weight average molecular weight of the component (B) is preferably in the range of 1,500 to 500,000, or 1,500 to 100,000.
  • the ratio of component (A) to component (B) in the adhesive can be any ratio. Furthermore, in order to ensure good releasability, it is desirable that the component (B) is contained at 5 or more by mass%, and in order to maintain the mechanical properties of the adhesive, the component (B) is at most 70 by mass Is desirable.
  • the ratio of component (A) to component (B) in the adhesive can be 95: 5 to 30:70 by mass%.
  • a method of bonding a laminate in which the adhesive is applied on a first substrate to form an adhesive layer, the second substrate is bonded, and heating is performed from the first substrate side.
  • the adhesive cures upon heating.
  • a bonding method may be mentioned in which the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  • Another example is a bonding method in which the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
  • Examples of the wafer include a silicon wafer having a diameter of about 300 mm and a thickness of about 770 ⁇ m.
  • Examples of the support (carrier) include glass wafers and silicon wafers having a diameter of about 300 mm and a thickness of about 700 mm.
  • the formation of the adhesive layer adheres the adhesive on the support, for example, by a spin coater to form an adhesive layer.
  • the adhesive may be bonded so as to sandwich the adhesive between the support and the circuit surface of the wafer, and heated at a temperature of 120 to 260 ° C. to cure the adhesive, thereby forming a laminate.
  • the adhesive is attached to the circuit surface with the back side of the wafer facing down by a spin coater to form an adhesive layer, and the support is bonded so as to sandwich the adhesive, and heated at a temperature of 120 to 260 ° C.
  • the adhesive can then be cured to form a laminate.
  • the curing of the adhesive starts from about 120 ° C., and the temperature may be 260 ° C. or higher, but it is preferably 260 ° C. or lower, for example 150 ° C. from the viewpoint of the heat resistance of the circuit surface (device surface) of the wafer.
  • the temperature can be set to about ° C to 220 ° C, or about 190 ° C to 200 ° C.
  • the heating time is preferably 1 minute or more from the viewpoint of bonding of the wafer by curing, and further preferably 5 minutes or more from the viewpoint of stabilization of the physical properties of the adhesive. For example, it can be 1 to 180 minutes, or 5 to 120 minutes.
  • the apparatus may use a hot plate, an oven or the like.
  • the adhesive can add a solvent for viscosity adjustment.
  • Aliphatic hydrocarbons, aromatic hydrocarbons, ketones and the like can be used.
  • the solvent is, for example, hexane, heptane, octane nonane, decane, undecane, dodecane, isododecane, mentane, limonene, toluene, xylene, methycylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone etc. can be used.
  • a support and a wafer formed so as to sandwich the adhesive layer can combine these objects under reduced pressure (for example, reduced pressure of 10 Pa to 10000 Pa) to form a laminate.
  • reduced pressure for example, reduced pressure of 10 Pa to 10000 Pa
  • heating for example, 30 ° C. to 100 ° C.
  • reduced pressure for example, 30 ° C. to 100 ° C.
  • the adhesive is applied on a first substrate to form an adhesive layer, the second substrate is joined and heated, and the adhesive is cured to form a laminate, and then the laminate is processed to form a first substrate,
  • a peeling method which causes peeling between the second substrate and the adhesive layer (the first substrate, the interface between the second substrate and the adhesive) may be mentioned.
  • the above peeling method may be mentioned in which the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  • the above-mentioned peeling method may be mentioned in which the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
  • the film thickness of the adhesive layer to which the above adhesive is applied can be 5 to 500 ⁇ m, 10 to 200 ⁇ m, 20 to 150 ⁇ m, 30 to 120 ⁇ m, or 30 to 70 ⁇ m.
  • the processing on the opposite side of the circuit surface of the wafer includes thinning of the wafer by polishing. Thereafter, through silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a laminated body of wafers, which is three-dimensionally mounted. In addition, the formation of a wafer back surface electrode and the like is also performed before and after that. While wafer thinning and TSV processes are heated to 250 to 350 ° C while bonded to a support, laminates as temporary adhesives used in the present invention have their heat resistance. There is.
  • a wafer with a diameter of about 300 mm and a thickness of about 770 ⁇ m can be thinned to a thickness of about 80 ⁇ m to 4 ⁇ m by polishing the back surface opposite to the circuit surface.
  • Peeling methods include solvent peeling, laser peeling, mechanical peeling with an apparatus having a sharp part, peeling between a support and a wafer, and the like.
  • the resin When the resin remains on the surface of the wafer, the resin can be removed by solvent cleaning (dissolution, lift off), tape peeling, or the like.
  • the present invention is a method of processing a laminate which is bonded by the above method and polished after the back surface of the wafer and then peeled off by the above method.
  • Component (A) of Adhesive 22.49 kg of a base polymer (manufactured by Wacker Kemi Co., Ltd.) consisting of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa ⁇ s and a vinyl group-containing MQ resin as the polysiloxane (a1) 1.46 kg of SiH group-containing linear polydimethylsiloxane (made by Wacker Kemi) with a viscosity of 70 mPa ⁇ s as polysiloxane (a2), SiH group-containing linear polydimethylsiloxane with a viscosity of 100 mPa ⁇ s as polysiloxane (a2) 0.63 kg of Wacker Kemi Co., Ltd.
  • a base polymer manufactured by Wacker Kemi Co., Ltd.
  • (Adhesive 1) Component (A) 99% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., A mixture of 1 mass% (the ratio of the (A) component and the (B-1) component in the (B-1) component) under the trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 1).
  • m and n indicate the number of repeating units.
  • Adhesive 2 Component (A) 97.5% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (Gelest, Inc. Manufactured by trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s) 2.5 mass% (proportion of (A) component and (B-1) component in (B-1) component) The resulting mixture was mixed for 5 minutes with an autorotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: ARE-500) to prepare (adhesive 2).
  • an autorotation / revolution mixer manufactured by Shinky Co., Ltd., trade name: ARE-500
  • (Adhesive 3) Component (A) 95% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., A mixture of 5 mass% (the ratio of the component (A) to the component (B-1) in the component (B-1)) under the trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 3).
  • Adhesive 4 Component (A) 90% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 10% by mass (ratio of component (A) and component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd., brand name ARE-500), and produced (adhesive 4).
  • Adhesive 5 Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 15% by mass (ratio of component (A) to component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 5).
  • Adhesive 6 Component (A) 70% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 30% by mass (ratio of component (A) to component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd., brand name ARE-500), and produced (adhesive 6).
  • (Adhesive 7) Component (A) 50% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s) 50% by mass (the ratio of the (A) component and the (B-1) component in the (B-1) component) -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 7).
  • a revolution mixer made by Shinky Co., Ltd. make, brand name ARE-500
  • (Adhesive 8) Component (A) 30% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 70% by mass (ratio of component (A) and component (B-1) in component (B-1)) -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 8).
  • a revolution mixer made by Shinky Co., Ltd. make, brand name ARE-500
  • (Adhesive 9) Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-2)) and component (B-2) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1025, weight average molecular weight 25200, viscosity 500mm 2 / s 15% by mass (ratio of (A) component and (B-2) component in (B-2) component) mixture of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 9).
  • m and n indicate the number of repeating units.
  • (Adhesive 10) Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) and component (A)) and component (B-3) phenyl group-modified silicone (Shin-Etsu Chemical Co., Ltd.) KF 50-3000CS, weight average molecular weight 39,400, viscosity 3000 mm 2 / s) 15 mass% (ratio of component (A) to component (B-3) in component (B-3))
  • the mixture was mixed for 5 minutes with a revolution mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 10).
  • m and n indicate the number of repeating units.
  • Adhesive 11 Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-4)) and component (B-4) phenyl group-modified silicone (manufactured by MOMENTIVE, product name)
  • a mixture consisting of TSF 431, weight average molecular weight 1800, viscosity 100 mm 2 / s, 15 mass% (proportion of (A) component and (B-4) component in (B-4) component) The mixture was mixed for 5 minutes under the trade name ARE-500, manufactured by Shinky Co., to prepare (adhesive 11).
  • ARE-500 manufactured by Shinky Co.
  • Adhesive 12 Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-5)) and component (B-5) phenyl group-modified silicone (manufactured by MOMENTIVE, product name)
  • Adhesive (Adhesive 12) was prepared by mixing for 5 minutes under the trade name ARE-500, manufactured by Shinky.
  • ARE-500 trade name
  • (Adhesive 13) Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-6)) and component (B-6) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PDM-0421, weight average molecular weight 6200, viscosity 100 mm 2 / s 15% by mass (ratio of (A) component and (B-6) component in (B-6) component) a mixture consisting of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 13).
  • m and n each represent the number of repeating units.
  • (Adhesive 14) Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-7)) and component (B-7) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PDM-0821, weight average molecular weight 8600, viscosity 125 mm 2 / s 15% by mass (ratio of (A) component and (B-7) component in (B-7) component) a mixture consisting of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 14).
  • m and n represent the number of repeating units.
  • Example 1 As a wafer on the device side, a 300 mm silicone wafer (thickness: 770 ⁇ m), and the above adhesive (1) to (8) by spin coating to form a temporary adhesive layer, each having a film thickness of about 50 ⁇ m. A film was formed on the surface to form the adhesive layers (1) to (8). A vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 ⁇ m) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck inside and produced the layered product.
  • a vacuum bonding apparatus manufactured by Suse Microtech Co., Ltd.
  • peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled.
  • Example 2 As a wafer on the device side, a 300 mm silicone wafer (thickness: 770 ⁇ m) was spin coated to form the above adhesive (5) with a film thickness of about 50 ⁇ m on the circuit surface of three wafers to form a temporary adhesive layer. The films were formed into adhesive layers (5-1) to (5-3), respectively.
  • a vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 ⁇ m) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck inside and produced the layered product. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes on a hot plate.
  • peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled.
  • the "carrier" and the one that could not be peeled off was regarded as "poor".
  • the adhesive layers (5-1) to (5-3) formed of the adhesive (5) showed good results in terms of peelability. Further, it was confirmed that the peeling interface was not changed by the heat treatment method performed at the time of curing of the adhesive, and that peeling was possible at the interface of the carrier and the adhesive.
  • the above adhesive (5) is formed on the circuit surface of the wafer with a film thickness of about 100 ⁇ m by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 ⁇ m) as a wafer on the device side.
  • Adhesive layer (5-7).
  • the laminates were produced in the following manner. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes so that the device-side wafer was on the hot plate.
  • peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled.
  • the "carrier” and the one that could not be peeled off was described as "x" as a defect.
  • Example 4 The above adhesive (5) is formed on the circuit surface of four wafers with a film thickness of about 50 ⁇ m by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 ⁇ m) as a wafer on the device side.
  • the membranes were formed into adhesive layers (5-8) to (5-11), respectively.
  • a vacuum bonding apparatus manufactured by Suse Microtech Co., Ltd.
  • the laminates were produced in the following manner. After that, heat treatment was performed at 120 ° C., 150 ° C., 220 ° C., and 260 ° C. for 10 minutes so that the device-side wafer was on the hot plate.
  • peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled.
  • the "carrier” and the one that could not be peeled off was described as "x" as a defect.
  • Example 5 The above adhesive (5) and (9) to (14) with a thickness of about 50 ⁇ m are formed by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 ⁇ m) as a wafer on the device side.
  • the films were formed on the circuit surface of the wafer as adhesion layers (5-12) and (9) to (14), respectively.
  • a vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so as to sandwich the adhesive layer between the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 ⁇ m) as a wafer on the carrier side (support) It stuck together inside and produced the layered product.
  • Example 6 The above adhesive (5) is formed on the circuit surface of the wafer with a film thickness of about 50 ⁇ m by spin coating to form a temporary adhesive layer on a trimmed silicon wafer (thickness: 770 ⁇ m) of 300 mm as a wafer on the device side.
  • the membrane was formed into an adhesive layer (5-13).
  • a vacuum bonding device manufactured by Suse Microtech, Inc., so that the above-mentioned adhesive layer is sandwiched between the wafer having the adhesive layer and a 300 mm silicon wafer (thickness: 770 ⁇ m) as a wafer (support) on the carrier side. ) Pasted together to make a laminate.
  • Example 7 Cleaning Test of Device Wafer As a wafer on the testing side of the device wafer, a temporary adhesive layer is formed on a global net 300 mm PI wafer (thickness: 770 ⁇ m, base: SiN + PI, scribe line: width 100 mm, 15 mm pitch)
  • the adhesive (5) was formed on the circuit surface of the wafer with a thickness of about 50 ⁇ m by spin coating to form an adhesive layer (5-14).
  • a vacuum bonding device (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 ⁇ m) as a wafer (support) on the carrier side sandwich the adhesive layer. ) Pasted together to make a laminate.
  • Example 8 As a wafer on the lift-off device side by tape, spin is used to form a temporary adhesive layer on 300 mm PI wafer (thickness: 770 ⁇ m, base: SiN + PI, scribe line: width 100 mm, 15 mm pitch)
  • the above adhesive (5) was formed into a film of about 50 ⁇ m thick on the circuit surface of the wafer by coating to form an adhesive layer (5-15).
  • a vacuum bonding device (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 ⁇ m) as a wafer (support) on the carrier side sandwich the adhesive layer. ) Pasted together to make a laminate.
  • an adhesive consisting only of the component (A) is applied to a thickness of about 50 ⁇ m to a 300 mm glass wafer (thickness: 770 ⁇ m) as a wafer on the carrier side (support), adhesive layer (A-1) ). Then, heat treatment was performed at 200 ° C. for 10 minutes.
  • a terminal masking tape made by Nitto Denko Corporation, trade name N-
  • the peeling test of the adhesive was carried out by the tape peeling method using 300). Attach the above tape to the adhesive surface of the carrier side wafer (support), peel off the tape from the carrier side wafer (support) at an angle in the range of 60 to 180 °, and the carrier side wafer (support) A test was conducted to separate the adhesive layers (5-15) and (A-1) from
  • Example 9 Regeneration test of carrier wafer (support) with solvent As a wafer on the test device side of 300 nm PI wafer (thickness: 770 ⁇ m, base: SiN + PI, scribe line: width 100 mm, pitch 15 mm) manufactured by Globalnet Inc.
  • the above-mentioned adhesive (5) was formed on the circuit surface of the wafer with a film thickness of about 50 ⁇ m by spin coating to form an adhesive layer (5-16).
  • a vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 ⁇ m) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck together inside and produced the layered product.
  • an adhesive consisting only of the component (A) is applied to a thickness of about 50 ⁇ m to a 300 mm glass wafer (thickness: 770 ⁇ m) as a wafer on the carrier side (support), adhesive layer (A-2) ). Then, heat treatment was performed at 200 ° C. for 10 minutes.
  • the adhesive layer (5-16) remaining on the wafer on the carrier side (support), and (A-2) are made of Isoper-E (hydrocarbon solvent manufactured by Ando Parachemy Co., Ltd.) and Shellsol MC421 (Shell Chemicals Japan)
  • the resultant was immersed in a hydrocarbon-based solvent (manufactured by Kabushiki Kaisha, Ltd.) to remove the adhesive layer with the solvent.
  • the case where the adhesion layer was able to be removed by lift-off after immersion in a solvent was evaluated as good and indicated by “o”, and the case where removal by lift-off was not possible was indicated by “x”.
  • Table 9 (Results of Example 9) ⁇ Isoper-E Shersol MC421 Adhesive layer (5-16) ⁇ ⁇ Adhesive layer (A-2) ⁇ ⁇ ⁇ ⁇
  • the laminate according to the present invention has a temporary adhesive layer between the support (support substrate) and the wafer as an additive, and the adhesive forming the temporary adhesive layer is a polyorganosiloxane component cured by a hydrosilylation reaction, It contains an adhesive containing a phenyl group-containing polyorganosiloxane component as an additive.

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Abstract

Provided are: a temporary adhesive agent which has excellent spin-coatability onto a circuit surface of a wafer or a support, also has excellent heat resistance during the bonding to an adhesive layer or during the processing of a rear surface of a wafer, can be removed easily after the polishing of a rear surface of a wafer, and makes it possible to remove an adhesive agent adhered onto a wafer or a support after removing of the temporary adhesive agent; a laminate containing the temporary adhesive agent; and a processing method using the temporary adhesive agent. An adhesive agent which can removably adhere between a support and a circuit surface of a wafer and can be used in the processing of a rear surface of a wafer, the adhesive agent being characterized by containing a component (A) that can be cured through a hydroxylation reaction and a component (B) that contains a phenyl-group-containing polyorganosiloxane, wherein the ratio of the content of the component (A) in % by mass to the content of the component (B) in % by mass is 95:5 to 30:70. The adhesive agent is applied onto a first substrate to form an adhesive layer, then a second substrate is bonded to the adhesive layer, and then the resultant laminate is heated from the first substrate side to cure the adhesive layer. After the completion of the processing of the laminate, delamination is allowed to cause between the first substrate and the adhesive layer and between the second substrate and the adhesive layer.

Description

フェニル基含有ポリシロキサンを含有する仮接着剤Temporary adhesive containing phenyl group-containing polysiloxane
本発明は、ウエハー裏面の研磨時にウエハーを支持体に固定するための仮接着剤とそれを用いた積層体に関する。 The present invention relates to a temporary adhesive for fixing a wafer to a support during polishing of the back surface of the wafer and a laminate using the same.
従来２次元的な平面方向に集積してきた半導体ウエハーは、より一層の集積化を目的に平面を更に３次元方向にも集積（積層）する半導体集積技術が求められている。この３次元積層はシリコン貫通電極（ＴＳＶ：ｔｈｒｏｕｇｈ　ｓｉｌｉｃｏｎ　ｖｉａ）によって結線しながら多層に集積していく技術である。多層に集積する際に、集積されるそれぞれのウエハーは形成された回路面とは反対側（即ち、裏面）を研磨によって薄化し、薄化された半導体ウエハーを積層する。 In the semiconductor wafer which has conventionally been integrated in a two-dimensional planar direction, there is a demand for a semiconductor integration technology in which the plane is further integrated (stacked) in the three-dimensional direction for the purpose of further integration. This three-dimensional lamination is a technology of integrating in multiple layers while connecting by means of through silicon vias (TSVs). In the case of integration in multiple layers, each wafer to be integrated is thinned by polishing on the side opposite to the formed circuit surface (i.e., the back surface), and the thinned semiconductor wafers are stacked.
薄化前の半導体ウエハー（ここでは単にウエハーとも呼ぶ）を、研磨装置で研磨するために支持体に接着される。その際の接着は研磨後に半導体ウエハーを容易に剥離されなければならないため、仮接着と呼ばれる。この仮接着は支持体から容易に取り外されなければならず、取り外しに大きな力を加えると薄化された半導体ウエハーは、切断されたり、変形したりすることがあり、その様なことが生じない様に、容易に取り外される。しかし、半導体ウエハーの裏面研磨時に研磨応力によって外れたりずれたりすることも好ましくない。従って、仮接着に求められる性能は研磨時の応力に耐え、研磨後に容易に取り外されることである。 A semiconductor wafer (also referred to herein as just a wafer) before thinning is bonded to a support for polishing in a polishing apparatus. The adhesion at that time is called temporary adhesion because the semiconductor wafer must be easily peeled off after polishing. This temporary bond must be easily removed from the support, and if a large force is applied for removal, the thinned semiconductor wafer may be cut or deformed, which does not occur. As well, easily removed. However, it is also not preferable that the semiconductor wafer is dislodged or deviated by polishing stress at the time of back surface polishing. Therefore, the performance required for temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.
例えば研磨時の平面方向に対して高い応力（強い接着力）を持ち、取り外し時の縦方向に対して低い応力（弱い接着力）を有する性能が求められる。 For example, it is required to have the ability to have high stress (strong adhesive force) in the planar direction at the time of polishing and low stress (weak adhesive force) in the longitudinal direction at the time of removal.
この様な接着プロセスとして、接着層と分離層を持ち、分離層がジメチルシロキサンのプラズマ重合によって形成され、研磨後に機械的に分離する方法（特許文献１、特許文献２参照）、
支持基板と半導体ウエハーとを接着性組成物で接着し、半導体ウエハーの裏面を研磨した後に接着剤をエッチング液で除去する方法（特許文献３参照）、並びに
支持体と半導体ウエハーを接着する接着層としては、アルケニル基含有オルガノポリシロキサンとヒドロシリル基含有オルガノポリシロキサンとを白金触媒で重合した重合層と、熱硬化性ポリシロキサンからなる重合層との組み合わせを含むウエハー加工体（特許文献４、特許文献５参照、特許文献６参照、特許文献７参照）、が開示されている。 As such an adhesion process, a method having an adhesion layer and a separation layer, wherein the separation layer is formed by plasma polymerization of dimethylsiloxane and mechanically separated after polishing (see Patent Document 1 and Patent Document 2),
A method of bonding a support substrate and a semiconductor wafer with an adhesive composition, polishing the back surface of the semiconductor wafer and then removing the adhesive with an etching solution (see Patent Document 3), and an adhesive layer for bonding the support and the semiconductor wafer A processed wafer comprising a combination of a polymerization layer obtained by polymerizing an alkenyl group-containing organopolysiloxane and a hydrosilyl group-containing organopolysiloxane with a platinum catalyst and a polymerization layer formed of a thermosetting polysiloxane (Patent Document 4, Patent Reference 5 and Patent Document 6 and Patent Document 7 are disclosed.
特表２０１２－５１０７１５Special table 2012-510715 特表２０１２－５１３６８４Special table 2012-513684 特表２００８－５３２３１３Special Table 2008-532313 特開２０１３－１７９１３５JP 2013-179135 特開２０１３－２３２４５９JP 2013-232459 特開２００６－５０８５４０Japanese Patent Application Publication No. 2006-508540 特開２００９－５２８６８８JP 2009-528688
ウエハーの回路面や、支持体へのスピンコート性に優れ、接着層との接合時やウエハー裏面の加工時における耐熱性に優れ、ウエハー裏面の研磨後には容易に剥離でき、剥離後はウエハーや支持体に付着した接着剤が簡単に除去できる仮接着剤及びその積層体、それを用いた加工方法を提供するものである。 Excellent spin coatability to the circuit surface of the wafer and the support, excellent heat resistance at the time of bonding with the adhesive layer and processing of the wafer back surface, it can be easily peeled off after polishing the wafer back surface, and after peeling off the wafer or wafer The temporary adhesive which can easily remove the adhesive attached to the support, the laminate thereof, and the processing method using the same.
本願発明は第１観点として、支持体とウエハーの回路面との間で剥離可能に接着し、ウエハーの裏面を加工するための接着剤であり、前記接着剤がヒドロシリル化反応により硬化する成分（Ａ）と、フェニル基含有ポリオルガノシロキサンとを含む成分（Ｂ）とを含み、成分（Ａ）と成分（Ｂ）の質量％が９５：５～３０：７０の割合である前記接着剤、 The present invention is, as a first aspect, an adhesive for releasably bonding between a support and a circuit surface of a wafer and processing the back surface of the wafer, wherein the adhesive cures by a hydrosilylation reaction ((1) The adhesive containing A) and a component (B) containing a phenyl group-containing polyorganosiloxane, wherein the weight percentage of the component (A) and the component (B) is a ratio of 95: 5 to 30:70,
第２観点として、成分（Ａ）が、ＳｉＯ２で表されるシロキサン単位（Ｑ単位）、Ｒ１Ｒ２Ｒ３ＳｉＯ１／２で表されるシロキサン単位（Ｍ単位）、Ｒ４Ｒ５ＳｉＯ２／２で表されるシロキサン単位（Ｄ単位）、及びＲ６ＳｉＯ３／２で表されるシロキサン単位（Ｔ単位）からなる群より選ばれるポリシロキサン（但しＲ１乃至Ｒ６はそれぞれＳｉ－Ｃ結合又はＳｉ－Ｈ結合によりケイ素原子に結合しているものである。）を含み、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と炭素原子数２～１０のアルケニル基を含むポリオルガノシロキサン（ａ１）と、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と水素原子を含むポリオルガノシロキサン（ａ２）とを含むポリシロキサン（Ａ１）と、白金族金属系触媒（Ａ２）とを含むものである第１観点に記載の接着剤、 As a second aspect, component (A), siloxane units (Q units) represented by SiO 2, siloxane units (M units) represented by R 1 R 2 R 3 SiO 1/2 , R 4 R 5 SiO A polysiloxane selected from the group consisting of a siloxane unit (D unit) represented by 2/2 and a siloxane unit (T unit) represented by R 6 SiO 3/2 (wherein R 1 to R 6 each represent Si— And the monovalent chemical group represented by R 1 to R 6 is an alkyl group having 1 to 10 carbon atoms and the number of carbon atoms, each of which is a C bond or a Si—H bond. Polyorganosiloxane (a1) containing alkenyl group of 2 to 10, and polyorganosiloxane (a2) containing monovalent alkyl group having 1 to 10 carbon atoms and hydrogen atom each of which is represented by R 1 to R 6 The adhesive according to the first aspect, which comprises a polysiloxane (A1) containing the above, and a platinum group metal-based catalyst (A2),
第３観点として、前記成分（Ｂ）が、（ｂ１）フェニルメチルシロキサン単位構造又はジフェニルシロキサン単位構造と、（ｂ２）ジメチルシロキサン単位構造との組み合わせである第１観点又は第２観点に記載の接着剤、 As the third aspect, the adhesive according to the first aspect or the second aspect, wherein the component (B) is a combination of (b1) phenylmethylsiloxane unit structure or diphenylsiloxane unit structure and (b2) dimethylsiloxane unit structure Agent,
第４観点として、加工がウエハーの裏面研磨である第１観点乃至第３観点のいずれか一つに記載の接着剤、 As a fourth aspect, the adhesive according to any one of the first to third aspects, wherein the processing is polishing the back surface of a wafer,
第５観点として、第一基体上に第１観点乃至第４観点のいずれか一つに記載の接着剤を塗布し接着層を形成し、第二基体を接合し、第一基体側から加熱する積層体の接合方法、 As a fifth aspect, the adhesive according to any one of the first to fourth aspects is applied onto a first substrate to form an adhesive layer, and a second substrate is joined and heated from the first substrate side Bonding method of laminates,
第６観点として、第一基体が支持体であり、第二基体がウエハーであり、ウエハーの回路面が第一基体と向き合うものである第５観点に記載の接合方法、 As a sixth aspect, the bonding method according to the fifth aspect, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
第７観点として、第一基体がウエハーであり、第二基体が支持体であり、ウエハーの回路面が第二基体と向き合うものである第５観点に記載の接合方法、 As a seventh aspect, the bonding method according to the fifth aspect, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
第８観点として、第一基体上に第１観点乃至第３観点のいずれか一つに記載の接着剤を塗布し接着層を形成し、第二基体を接合し、第一基体側から加熱し接着剤を硬化させ積層体を形成した後に、積層体を加工し、第一基体、第二基体と接着層の間で剥離を生じる剥離方法、 As an eighth aspect, the adhesive according to any one of the first to third aspects is coated on a first substrate to form an adhesive layer, a second substrate is joined, and heating is performed from the first substrate side. After curing the adhesive to form a laminate, the laminate is processed, and a peeling method which causes peeling between the first substrate, the second substrate and the adhesive layer,
第９観点として、第一基体上に第４観点に記載の接着剤を塗布し接着層を形成し、第二基体を接合し、第一基体側から加熱し接着剤を硬化させ積層体を形成した後に、積層体を加工し、第一基体、第二基体と接着層の間で剥離を生じる剥離方法、 As a ninth aspect, the adhesive described in the fourth aspect is coated on the first substrate to form an adhesive layer, the second substrate is joined, and the adhesive is cured by heating from the first substrate side to form a laminate. And processing the laminate to form a peeling between the first substrate, the second substrate and the adhesive layer,
第１０観点として、第一基体が支持体であり、第二基体がウエハーであり、ウエハーの回路面が第一基体と向き合うものである第８観点に記載の剥離方法、 As a tenth aspect, the peeling method according to the eighth aspect, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate,
第１１観点として、第一基体が支持体であり、第二基体がウエハーであり、ウエハーの回路面が第一基体と向き合うものである第９観点に記載の剥離方法、 As an eleventh aspect, the peeling method according to the ninth aspect, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate,
第１２観点として、第一基体がウエハーであり、第二基体が支持体であり、ウエハーの回路面が第二基体と向き合うものである第８観点に記載の剥離方法、 As a twelfth aspect, the peeling method according to the eighth aspect, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
第１３観点として、第一基体がウエハーであり、第二基体が支持体であり、ウエハーの回路面が第二基体と向き合うものである第９観点に記載の剥離方法、 As a thirteenth aspect, the peeling method according to the ninth aspect, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate,
第１４観点として、加工がウエハーの裏面研磨である第８、１０、１２観点のいずれか一つに記載の剥離方法である。 According to a fourteenth aspect, in the peeling method according to any one of the eighth, tenth, and twelfth aspects, the processing is polishing the back surface of the wafer.
本発明では、支持体とウエハーの回路面との間で剥離可能に接着しウエハーの裏面を加工するための接着剤であり、ヒドロシリル化反応により硬化することを特徴とする成分（Ａ）と、フェニル基含有ポリオルガノシロキサン成分（Ｂ）とを含むことを、特徴とする接着剤（仮接着剤）を提供する。 In the present invention, the component (A) is an adhesive for releasably bonding between a support and a circuit surface of a wafer to process the back surface of the wafer, and curing by a hydrosilylation reaction, An adhesive (temporary adhesive) characterized by including a phenyl group-containing polyorganosiloxane component (B) is provided.
支持体とウエハーの回路面との間に装入される仮接着剤として、ヒドロシリル化反応により架橋硬化する成分（Ａ）と、フェニル基を持つ成分（Ｂ）とを含み、ウエハーの回路面の反対側のウエハー裏面を加工するための積層体であり、特定成分のポリシロキサンを組み合わせたことにより、ウエハーの回路面へのスピンコート性に優れ、接着層との接合時やウエハー裏面の加工時における耐熱性に優れ、ウエハーの裏面の加工後、即ち研磨後には容易に剥離でき、剥離後はウエハーや支持体に付着した接着剤が溶剤またはテープによって簡単に除去できるという効果が得られる。 The temporary adhesive loaded between the support and the circuit surface of the wafer includes a component (A) that crosslinks and hardens by a hydrosilylation reaction, and a component (B) having a phenyl group; It is a laminate for processing the back side of the wafer on the opposite side, and by combining polysiloxane of a specific component, it excels in spin coatability to the circuit side of the wafer, and when bonding with adhesive layer or processing the back side of wafer It is possible to easily peel off after processing the back surface of the wafer, that is, after polishing, and after peeling off, the adhesive agent attached to the wafer or the support can be easily removed by a solvent or a tape.
ウエハーの回路面の反対側の加工とは、研磨によるウエハーの薄化が行われる。その後、シリコン貫通電極（ＴＳＶ）等の形成を行い、その後に支持体から薄化ウエハーを剥離してウエハーの積層体を形成し、３次元実装化される。また、それに前後してウエハー裏面電極等の形成も行われる。ウエハーの薄化とＴＳＶプロセスには支持体に接着された状態で２５０～３５０℃の熱が付加されるが、本発明に用いられる接着剤としての積層体はそれらの耐熱性を有している。 The processing on the opposite side of the circuit surface of the wafer involves thinning of the wafer by polishing. Thereafter, through silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a laminated body of wafers, which is three-dimensionally mounted. In addition, the formation of a wafer back surface electrode and the like is also performed before and after that. While wafer thinning and TSV processes are subjected to heat at 250-350 ° C while bonded to a support, laminates as adhesives used in the present invention have their heat resistance .
本願発明は支持体とウエハーの回路面との間で剥離可能に接着しウエハーの裏面を加工するための接着剤であり、上記接着剤がヒドロシリル化反応により硬化する成分（Ａ）とフェニル基含有ポリオルガノシロキサンとを含む成分（Ｂ）とを含み、成分（Ａ）と成分（Ｂ）の質量％が９５：５～３０：７０の割合である上記接着剤である。 The present invention is an adhesive for releasably bonding between a support and a circuit surface of a wafer and processing the back surface of the wafer, wherein the adhesive cures by a hydrosilylation reaction and contains a component (A) and a phenyl group. It is the above-mentioned adhesive, which comprises a component (B) containing a polyorganosiloxane and the ratio by mass of the component (A) to the component (B) is 95: 5 to 30:70.
本発明では接着剤によって支持体とウエハーが仮接着され、ウエハーの回路面とは反対側の裏面が研磨等によって加工されることにより、ウエハーの厚みを薄化することができる。 In the present invention, the thickness of the wafer can be reduced by temporarily bonding the support and the wafer with an adhesive and processing the back surface of the wafer opposite to the circuit surface by polishing or the like.
上記仮接着はウエハー裏面の研磨時は接着されていて、ウエハー裏面の研磨後には支持体と薄化されたウエハーが分離できるものである。 The temporary adhesion is performed when the back of the wafer is polished, and after the back of the wafer is polished, the support and the thinned wafer can be separated.
ここで剥離可能とは、他の剥離箇所よりも剥離強度が低く、剥離しやすいことを示す。 Here, "peelable" means that the peel strength is lower than at other peel points, and it is easy to peel.
本発明で接着層は、接着剤によって形成される。接着剤は成分（Ａ）と成分（Ｂ）とを含み、更にその他の添加物を含むことができる。 In the present invention, the adhesive layer is formed by an adhesive. The adhesive contains the component (A) and the component (B), and may further contain other additives.
成分（Ａ）が、ＳｉＯ２で表されるシロキサン単位（Ｑ単位）、Ｒ１Ｒ２Ｒ３ＳｉＯ１／２で表されるシロキサン単位（Ｍ単位）、Ｒ４Ｒ５ＳｉＯ２／２で表されるシロキサン単位（Ｄ単位）、及びＲ６ＳｉＯ３／２で表されるシロキサン単位（Ｔ単位）からなる群より選ばれるポリシロキサン（但しＲ１乃至Ｒ６はそれぞれＳｉ－Ｃ結合又はＳｉ－Ｈ結合によりケイ素原子に結合しているものである。）を含み、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と炭素原子数２～１０のアルケニル基を含むポリオルガノシロキサン（ａ１）と、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と水素原子を含むポリオルガノシロキサン（ａ２）とを含むポリシロキサン（Ａ１）と、白金族金属系触媒（Ａ２）とを含むものである。 Component (A) is a siloxane unit represented by SiO 2 (Q unit), a siloxane unit represented by R 1 R 2 R 3 SiO 1/2 (M unit), R 4 R 5 SiO 2/2 Selected from the group consisting of the siloxane unit (D unit) and the siloxane unit (T unit) represented by R 6 SiO 3/2 (wherein R 1 to R 6 each represent a Si—C bond or Si— And the monovalent chemical group represented by R 1 to R 6 is an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. A polysiloxane comprising a polyorganosiloxane (a1) containing a group and a polyorganosiloxane (a2) wherein the monovalent chemical group represented by R 1 to R 6 contains an alkyl group having 1 to 10 carbon atoms and a hydrogen atom, respectively It contains a xanthan (A1) and a platinum group metal-based catalyst (A2).
ポリシロキサン（Ａ１）はポリオルガノシロキサン（ａ１）とポリオルガノシロキサン（ａ２）を含む。ポリオルガノシロキサン（ａ１）が炭素原子数１～１０のアルキル基と炭素原子数２～１０のアルケニル基を含んでいて、ポリオルガノシロキサン（ａ２）が炭素原子数１～１０のアルキル基と水素原子を含んでいる。アルケニル基とＳｉ－Ｈ基が白金族金属系触媒（Ａ２）によりヒドロシリル化反応によって架橋構造を形成し硬化する。 Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). The polyorganosiloxane (a1) contains an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and the polyorganosiloxane (a2) has an alkyl group having 1 to 10 carbon atoms and a hydrogen atom Contains. The alkenyl group and the Si-H group form a crosslinked structure by the hydrosilylation reaction with the platinum group metal catalyst (A2) and cure.
ポリオルガノシロキサン（ａ１）はＱ単位、Ｍ単位、Ｄ単位、Ｔ単位から選ばれるが、例えば（Ｑ単位とＭ単位）と（Ｄ単位とＭ単位）との組み合わせ、（Ｔ単位とＭ単位）と（Ｄ単位とＭ単位）との組み合わせ、（Ｑ単位とＴ単位とＭ単位）と（Ｔ単位とＭ単位）との組み合わせ、（Ｔ単位とＭ単位）の組み合わせ、（Ｑ単位とＭ単位）の組み合わせによって形成することができる。 The polyorganosiloxane (a1) is selected from Q unit, M unit, D unit and T unit, for example, a combination of (Q unit and M unit) and (D unit and M unit), (T unit and M unit) Combination of (D unit and M unit), combination of (Q unit, T unit and M unit) and (T unit and M unit), combination of (T unit and M unit), (Q unit and M unit) Can be formed by a combination of
ポリオルガノシロキサン（ａ２）はＱ単位、Ｍ単位、Ｄ単位、Ｔ単位から選ばれるが、例えば（Ｍ単位とＤ単位）の組み合わせ、（Ｑ単位とＭ単位）の組み合わせ、（Ｑ単位とＴ単位とＭ単位）の組み合わせによって形成することができる。 The polyorganosiloxane (a2) is selected from Q unit, M unit, D unit, T unit, for example, a combination of (M unit and D unit), a combination of (Q unit and M unit), (Q unit and T unit) And M units) can be formed.
上記炭素原子数２～１０のアルケニル基は、例えばエテニル基、１－プロペニル基、２－プロペニル基、１－メチル－１－エテニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、２－メチル－１－プロペニル基、２－メチル－２－プロペニル基、１－エチルエテニル基、１－メチル－１－プロペニル基、１－メチル－２－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、１－ｎ－プロピルエテニル基、１－メチル－１－ブテニル基、１－メチル－２－ブテニル基、１－メチル－３－ブテニル基、２－エチル－２－プロペニル基、２－メチル－１－ブテニル基、２－メチル－２－ブテニル基、２－メチル－３－ブテニル基、３－メチル－１－ブテニル基、３－メチル－２－ブテニル基、３－メチル－３－ブテニル基、１,１－ジメチル－２－プロペニル基、１－i－プロピルエテニル基、１,２－ジメチル－１－プロペニル基、１,２－ジメチル－２－プロペニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、１－メチル－１－ペンテニル基、１－メチル－２－ペンテニル基、１－メチル－３－ペンテニル基、１－メチル－４－ペンテニル基、１－ｎ－ブチルエテニル基、２－メチル－１－ペンテニル基、２－メチル－２－ペンテニル基、２－メチル－３－ペンテニル基、２－メチル－４－ペンテニル基、２－ｎ－プロピル－２－プロペニル基、３－メチル－１－ペンテニル基、３－メチル－２－ペンテニル基、３－メチル－３－ペンテニル基、３－メチル－４－ペンテニル基、３－エチル－３－ブテニル基、４－メチル－１－ペンテニル基、４－メチル－２－ペンテニル基、４－メチル－３－ペンテニル基、４－メチル－４－ペンテニル基、１,１－ジペンテニルメチル－２－ブテニル基、１,１－ジメチル－３－ブテニル基、１,２－ジメチル－１－ブテニル基、１,２－ジメチル－２－ブテニル基、１,２－ジメチル－３－ブテニル基、１－メチル－２－エチル－２－プロペニル基、１－s－ブチルエテニル基、１,３－ジメチル－１－ブテニル基、１,３－ジメチル－２－ブテニル基、１,３－ジメチル－３－ブテニル基、１－i－ブチルエテニル基、２,２－ジメチル－３－ブテニル基、２,３－ジメチル－１－ブテニル基、２,３－ジメチル－２－ブテニル基、２,３－ジメチル－３－ブテニル基、２－i－プロピル－２－プロペニル基、３,３－ジメチル－１－ブテニル基、１－エチル－１－ブテニル基、１－エチル－２－ブテニル基、１－エチル－３－ブテニル基、１－ｎ－プロピル－１－プロペニル基、１－ｎ－プロピル－２－プロペニル基、２－エチル－１－ブテニル基、２－エチル－２－ブテニル基、２－エチル－３－ブテニル基、１,１,２－トリメチル－２－プロペニル基、１－t－ブチルエテニル基、１－メチル－１－エチル－２－プロペニル基、１－エチル－２－メチル－１－プロペニル基、１－エチル－２－メチル－２－プロペニル基、１－i－プロピル－１－プロペニル基及び１－i－プロピル－２－プロペニル基等が挙げられる。特に、エテニル基、即ちビニル基、２－プロペニル基、即ちアリル基を好ましく用いることができる。 The alkenyl group having 2 to 10 carbon atoms is, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-Methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group , 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl -2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group , -Methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group Group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4 -Pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group , 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1- Dipentenylmethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3- Butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl -3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3- Dimethyl-3-butenyl group, 2-i-propyl-2- Lopenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group Group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2- Propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1 And -i-propyl-1-propenyl group and 1-i-propyl-2-propenyl group. In particular, ethenyl group, that is, vinyl group, 2-propenyl group, that is, allyl group can be preferably used.
上記炭素原子数１～１０のアルキル基は、例えばメチル基、エチル基、ｎ－プロピル基、i－プロピル基、ｎ－ブチル基、i－ブチル基、ｓ－ブチル基、t－ブチル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１,１－ジメチル－ｎ－プロピル基、１,２－ジメチル－ｎ－プロピル基、２,２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１,１－ジメチル－ｎ－ブチル基、１,２－ジメチル－ｎ－ブチル基、１,３－ジメチル－ｎ－ブチル基、２,２－ジメチル－ｎ－ブチル基、２,３－ジメチル－ｎ－ブチル基、３,３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１,１,２－トリメチル－ｎ－プロピル基、１,２,２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基及び１－エチル－２－メチル－ｎ－プロピル基等が挙げられる。特にメチル基を好ましく用いることができる。 The alkyl group having 1 to 10 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-butyl group Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl- n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2 -Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl- -Butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1- Ethyl-1-methyl-n-propyl group and 1-ethyl-2-methyl-n-propyl group etc. may be mentioned. In particular, a methyl group can be preferably used.
ポリオルガノシロキサン（ａ１）は炭素原子数１～１０のアルキル基と炭素原子数２～１０のアルケニル基で構成され、炭素原子数１～１０のアルキル基がメチル基であり、炭素原子数２～１０のアルケニル基がエテニル基、即ちビニル基であって、アルケニル基がＲ１乃至Ｒ６で表す全置換基中に０．１モル％～５０．０モル％、好ましくは０．５モル％～３０．０モル％とすることができ、残りのＲ１乃至Ｒ６はアルキル基とすることができる。 The polyorganosiloxane (a1) is composed of an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms is a methyl group and has 2 to 6 carbon atoms The alkenyl group of 10 is an ethenyl group, that is, a vinyl group, and 0.1% by mole to 50.0% by mole, preferably 0.5% by mole, of all substituents represented by R 1 to R 6 in which the alkenyl group is represented by R 1 to R 6 It can be 30.0 mol%, and the remaining R 1 to R 6 can be alkyl groups.
また、ポリオルガノシロキサン（ａ２）は炭素原子数１～１０のアルキル基と水素原子で構成され、炭素原子数１～１０のアルキル基がメチル基であり、水素原子はＳｉ－Ｈの構造を形成する。水素原子、即ちＳｉ－Ｈ基がＲ１乃至Ｒ６で表す全置換基中に０．１モル％～５０．０モル％、好ましくは１０．０モル％～４０．０モル％とすることができ、残りのＲ１乃至Ｒ６はアルキル基とすることができる。 The polyorganosiloxane (a2) is composed of an alkyl group having 1 to 10 carbon atoms and a hydrogen atom, the alkyl group having 1 to 10 carbon atoms is a methyl group, and the hydrogen atom forms a structure of Si-H Do. Hydrogen atom, that is, 0.1 to 50.0 mol%, preferably 10.0 to 40.0 mol%, in all substituents represented by R 1 to R 6 in a hydrogen atom; The remaining R 1 to R 6 can be alkyl groups.
ポリオルガノシロキサン（ａ１）とポリオルガノシロキサン（ａ２）は、アルケニル基とＳｉ－Ｈ基で示される水素原子がモル比で、２．０：１．０好ましくは１．５：１．０の範囲に含有することができる。 In the polyorganosiloxane (a1) and the polyorganosiloxane (a2), the molar ratio of hydrogen atoms represented by the alkenyl group and the Si-H group is in the range of 2.0: 1.0, preferably 1.5: 1.0. Can be contained in
上記ポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）は、それぞれ重量平均分子量が５００～１００００００、又は５０００～５００００の範囲で用いることができる。 The polyorganosiloxane (a1) and the polyorganosiloxane (a2) can be used in a weight average molecular weight of 500 to 1,000,000, or 5,000 to 50,000, respectively.
成分（Ａ）は白金族金属系触媒（Ａ２）を含有する。白金系の金属触媒はアルケニル基とＳｉ－Ｈ基とのヒドロシリル化付加反応を促進するための触媒であり、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と１価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒が用いられる。白金とオレフィン類との錯体としては、例えばジビニルテトラメチルジシロキサンと白金との錯体が挙げられる。白金触媒の添加量はポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）の合計量に対して１．０～５０．０ｐｐｍの範囲で添加することができる。 Component (A) contains a platinum group metal catalyst (A2). A platinum-based metal catalyst is a catalyst for promoting the hydrosilylation addition reaction of an alkenyl group and a Si-H group, and is a reaction of platinum black, platinum chloride, platinum chloride acid, chloride acid and alcohol and monohydric alcohol. , Platinum-based catalysts such as complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate are used. Examples of complexes of platinum and olefins include complexes of divinyl tetramethyldisiloxane and platinum. The addition amount of the platinum catalyst can be added in the range of 1.0 to 50.0 ppm with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
成分（Ａ）は更にヒドロシリル化反応の進行を抑える抑制剤（Ａ３）としてアルキニルアルコールを添加することができる。抑制剤としては例えば、１－エチニル－１－シクロヘキサノール等が挙げられる。これら抑制剤はポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）に対して１０００．０～１００００．０ｐｐｍの範囲で添加することができる。 Component (A) can further add an alkynyl alcohol as an inhibitor (A3) to suppress the progress of the hydrosilylation reaction. Examples of the inhibitor include 1-ethynyl-1-cyclohexanol and the like. These inhibitors can be added in the range of 1000.0 to 10000.0 ppm with respect to the polyorganosiloxane (a1) and the polyorganosiloxane (a2).
本発明の成分（Ｂ）に用いられるポリオルガノシロキサンは、（ｂ１）フェニルメチルシロキサン単位構造又はジフェニルシロキサン単位構造と、（ｂ２）ジメチルシロキサン単位構造との組み合わせを用いることができる。 The polyorganosiloxane used for the component (B) of this invention can use the combination of (b1) phenyl methyl siloxane unit structure or diphenyl siloxane unit structure, and (b2) dimethylsiloxane unit structure.
上記（ｂ１）はＲ１Ｒ２ＳｉＯ２／２（但しＲ１及びＲ２はそれぞれＳｉ－Ｃ結合によりケイ素原子に結合している。）で表されるシロキサン単位（Ｄ単位）を含み、Ｒ１はフェニル基又は炭素原子数１～１０のアルキル基（特にメチル基が好ましい。）、Ｒ２はフェニル基である。 The above (b1) contains a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 (wherein R 1 and R 2 are each bonded to a silicon atom by a Si—C bond), 1 is a phenyl group or an alkyl group having 1 to 10 carbon atoms (particularly preferably a methyl group), and R 2 is a phenyl group.
上記（ｂ２）はＲ１Ｒ２ＳｉＯ２／２（但しＲ１及びＲ２はそれぞれＳｉ－Ｃ結合によりケイ素原子に結合している。）で表されるシロキサン単位（Ｄ単位）を含み、Ｒ１及びＲ２はそれぞれ炭素原子数１～１０のアルキル基（特にメチル基が好ましい。）である。 The above (b2) contains a siloxane unit (D unit) represented by R 1 R 2 SiO 2/2 (wherein R 1 and R 2 are each bonded to a silicon atom by a Si—C bond), 1 and R 2 each represent an alkyl group having 1 to 10 carbon atoms (in particular, a methyl group is preferable).
上記アルキル基は、好ましくはメチル基であり、フェニル基は連結基を介するか又は直接にケイ素原子に結合した構造を有する。 The alkyl group is preferably a methyl group, and the phenyl group has a structure bonded to a silicon atom via a linking group or directly.
成分（Ｂ）に用いられるポリオルガノシロキサンは、シロキサン単位（Ｄ単位）を含むが、Ｑ単位、Ｍ単位、Ｔ単位を含んでいても良い。例えば、Ｄ単位のみからなる場合、Ｄ単位とＱ単位の組み合わせの場合、Ｄ単位とＭ単位の組み合わせの場合、Ｄ単位とＴ単位の組み合わせの場合、Ｄ単位とＱ単位とＭ単位の組み合わせの場合、Ｄ単位とＭ単位とＴ単位の組み合わせの場合、Ｄ単位とＱ単位とＭ単位とＴ単位の組み合わせの場合等が挙げられる。 The polyorganosiloxane used for the component (B) contains siloxane units (D units), but may contain Q units, M units and T units. For example, when it consists only of D units, in the case of a combination of D units and Q units, in the case of a combination of D units and M units, in the case of a combination of D units and T units, a combination of D units, Q units and M units In the case of the combination of D unit, M unit and T unit, the combination of D unit, Q unit, M unit and T unit, etc. may be mentioned.
成分（Ｂ）の重量平均分子量は１５００～５０００００、又は１５００～１０００００の範囲が好ましい。 The weight average molecular weight of the component (B) is preferably in the range of 1,500 to 500,000, or 1,500 to 100,000.
接着性においては、接着剤中の成分（Ａ）と成分（Ｂ）の割合は任意の割合とすることが可能である。更に剥離性が良好であるためには、成分（Ｂ）が質量％で５以上含まれていることが望ましく、接着剤の力学物性を維持するために、成分（Ｂ）が質量％で７０以下であることが望ましい。接着剤中の成分（Ａ）と成分（Ｂ）の割合が質量％で９５：５～３０：７０とすることができる。 In terms of adhesion, the ratio of component (A) to component (B) in the adhesive can be any ratio. Furthermore, in order to ensure good releasability, it is desirable that the component (B) is contained at 5 or more by mass%, and in order to maintain the mechanical properties of the adhesive, the component (B) is at most 70 by mass Is desirable. The ratio of component (A) to component (B) in the adhesive can be 95: 5 to 30:70 by mass%.
本発明では、第一基体上に上記接着剤を塗布し接着層を形成し、第二基体を接合し、第一基体側から加熱する積層体の接合方法が挙げられる。加熱により接着剤が硬化する。 In the present invention, a method of bonding a laminate is provided in which the adhesive is applied on a first substrate to form an adhesive layer, the second substrate is bonded, and heating is performed from the first substrate side. The adhesive cures upon heating.
第一基体が支持体であり、第二基体がウエハーであり、ウエハーの回路面が第一基体と向き合うものである接合方法が挙げられる。 A bonding method may be mentioned in which the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
また、第一基体がウエハーであり、第二基体が支持体であり、ウエハーの回路面が第二基体と向き合うものである接合方法が挙げられる。 Another example is a bonding method in which the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
ウエハーとしては例えば直径３００ｍｍ、厚さ７７０μｍ程度のシリコンウエハーが挙げられる。 Examples of the wafer include a silicon wafer having a diameter of about 300 mm and a thickness of about 770 μm.
支持体（キャリア）としては例えば直径３００ｍｍ、厚さ７００ｍｍ程度のガラスウエハーやシリコンウエハーを挙げることができる。 Examples of the support (carrier) include glass wafers and silicon wafers having a diameter of about 300 mm and a thickness of about 700 mm.
接着層の形成は接着剤を例えばスピンコーターにより支持体上に付着させ、接着層を形成します。支持体とウエハーの回路面の間で接着剤を挟むように貼り合わせ、１２０～２６０℃の温度で加熱して接着剤を硬化させ、積層体を形成することができる。 The formation of the adhesive layer adheres the adhesive on the support, for example, by a spin coater to form an adhesive layer. The adhesive may be bonded so as to sandwich the adhesive between the support and the circuit surface of the wafer, and heated at a temperature of 120 to 260 ° C. to cure the adhesive, thereby forming a laminate.
また、接着剤をスピンコーターにより、ウエハーの裏面を下にして回路面に接着剤を付着させ接着層を形成し、支持体は接着剤を挟むように貼り合わせ、１２０～２６０℃の温度で加熱して接着剤を硬化させ、積層体を形成することができる。加熱温度は１２０℃程度から接着剤の硬化が始まり、２６０℃以上の温度にすることも可能であるが、ウエハーの回路面（デバイス面）の耐熱性の観点から２６０℃以下が好ましく、例えば１５０℃～２２０℃程度、又は１９０℃～２００℃程度とすることができる。加熱時間は、硬化によるウエハーの接合の観点から、１分間以上が望ましく、さらに接着剤の物性安定化の観点から５分間以上の加熱がさらに好ましい。例えば、１～１８０分間、又は５～１２０分間とすることができる。装置は、ホットプレート、オーブンなどが使用できる。 In addition, the adhesive is attached to the circuit surface with the back side of the wafer facing down by a spin coater to form an adhesive layer, and the support is bonded so as to sandwich the adhesive, and heated at a temperature of 120 to 260 ° C. The adhesive can then be cured to form a laminate. The curing of the adhesive starts from about 120 ° C., and the temperature may be 260 ° C. or higher, but it is preferably 260 ° C. or lower, for example 150 ° C. from the viewpoint of the heat resistance of the circuit surface (device surface) of the wafer. The temperature can be set to about ° C to 220 ° C, or about 190 ° C to 200 ° C. The heating time is preferably 1 minute or more from the viewpoint of bonding of the wafer by curing, and further preferably 5 minutes or more from the viewpoint of stabilization of the physical properties of the adhesive. For example, it can be 1 to 180 minutes, or 5 to 120 minutes. The apparatus may use a hot plate, an oven or the like.
また、接着剤は粘度調整のため溶剤を添加することができる。脂肪族炭化水素、芳香族炭化水素、ケトンなどが使用できる。その溶剤は例えば、ヘキサン、へプタン、オクタンノナン、デカン、ウンデカン、ドデカン、イソドデカン、メンタン、リモネン、トルエン、キシレン、メチシレン、クメン、ＭＩＢＫ（メチルイソブチルケトン）、酢酸ブチル、ジイソブチルケトン、２－オクタノン、２－ノナノン、５－ノナノンなどが使用できる。 Moreover, the adhesive can add a solvent for viscosity adjustment. Aliphatic hydrocarbons, aromatic hydrocarbons, ketones and the like can be used. The solvent is, for example, hexane, heptane, octane nonane, decane, undecane, dodecane, isododecane, mentane, limonene, toluene, xylene, methycylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone etc. can be used.
接着層を挟むように形成する支持体とウエハーは、これら物体を減圧下（例えば、１０Ｐａ～１００００Ｐａの減圧状態）に合体させ積層体を形成させることができる。支持体とウエハーを合体させるときは減圧下に加熱（例えば、３０℃～１００℃）して行うこともできる。 A support and a wafer formed so as to sandwich the adhesive layer can combine these objects under reduced pressure (for example, reduced pressure of 10 Pa to 10000 Pa) to form a laminate. When combining a support and a wafer, heating (for example, 30 ° C. to 100 ° C.) can also be performed under reduced pressure.
第一基体上に上記接着剤を塗布し接着層を形成し、第二基体を接合し、加熱し、上記接着剤を硬化させ積層体を形成した後に、積層体を加工し、第一基体、第二基体と接着層の間（第一基体、第二基体と接着剤の界面）で剥離を生じる剥離方法が挙げられる。 The adhesive is applied on a first substrate to form an adhesive layer, the second substrate is joined and heated, and the adhesive is cured to form a laminate, and then the laminate is processed to form a first substrate, A peeling method which causes peeling between the second substrate and the adhesive layer (the first substrate, the interface between the second substrate and the adhesive) may be mentioned.
第一基体が支持体であり、第二基体がウエハーであり、ウエハーの回路面が第一基体と向き合うものである上記の剥離方法が挙げられる。 The above peeling method may be mentioned in which the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
また、第一基体がウエハーであり、第二基体が支持体であり、ウエハーの回路面が第二基体と向き合うものである上記の剥離方法が挙げられる。 In addition, the above-mentioned peeling method may be mentioned in which the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
上記の接着剤を塗布する接着層の膜厚は５～５００μｍ、又は１０～２００μｍ、又は２０～１５０μｍ、又は３０～１２０μｍ、又は３０～７０μｍとすることができる。 The film thickness of the adhesive layer to which the above adhesive is applied can be 5 to 500 μm, 10 to 200 μm, 20 to 150 μm, 30 to 120 μm, or 30 to 70 μm.
ウエハーの回路面の反対側の加工とは、研磨によるウエハーの薄化が挙げられる。その後、シリコン貫通電極（ＴＳＶ）等の形成を行い、その後に支持体から薄化ウエハーを剥離してウエハーの積層体を形成し、３次元実装化される。また、それに前後してウエハー裏面電極等の形成も行われる。ウエハーの薄化とＴＳＶプロセスには支持体に接着された状態で２５０～３５０℃の熱が付加されるが、本発明に用いられる仮接着剤としての積層体はそれらの耐熱性を有している。 The processing on the opposite side of the circuit surface of the wafer includes thinning of the wafer by polishing. Thereafter, through silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support to form a laminated body of wafers, which is three-dimensionally mounted. In addition, the formation of a wafer back surface electrode and the like is also performed before and after that. While wafer thinning and TSV processes are heated to 250 to 350 ° C while bonded to a support, laminates as temporary adhesives used in the present invention have their heat resistance. There is.
例えば直径３００ｍｍ、厚さ７７０μｍ程度のウエハーは、回路面とは反対の裏面を研磨して、厚さ８０μｍ～４μｍ程度まで薄化することができる。 For example, a wafer with a diameter of about 300 mm and a thickness of about 770 μm can be thinned to a thickness of about 80 μm to 4 μm by polishing the back surface opposite to the circuit surface.
接着し、裏面の加工（研磨）を行った後に、支持体とウエハーを剥離する。剥離方法は溶剤剥離、レーザー剥離、鋭部を有する機材で機械的に剥離、支持体とウエハーの間で引きはがす剥離等が挙げられる。 After bonding and processing (polishing) of the back side, the support and the wafer are peeled off. Peeling methods include solvent peeling, laser peeling, mechanical peeling with an apparatus having a sharp part, peeling between a support and a wafer, and the like.
ウエハーの表面に樹脂が残存した場合、溶剤による洗浄(溶解、リフトオフ)、テープピーリングなどにより樹脂を除去することができる。 When the resin remains on the surface of the wafer, the resin can be removed by solvent cleaning (dissolution, lift off), tape peeling, or the like.
本発明は上記方法で接合し、ウエハーの裏面を研磨後、上記方法で剥離する積層体の加工方法である。 The present invention is a method of processing a laminate which is bonded by the above method and polished after the back surface of the wafer and then peeled off by the above method.
接着剤の成分（Ａ）の調製
ポリシロキサン（ａ１）として粘度２００ｍＰａ・ｓのビニル基含有直鎖状ポリジメチルシロキサンとビニル基含有のＭＱ樹脂とからなるベースポリマー（ワッカーケミ社製）２２．４９ｋｇ、ポリシロキサン（ａ２）として粘度７０ｍＰａ・ｓのＳｉＨ基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）１．４６ｋｇ、ポリシロキサン（ａ２）として粘度１００ｍＰａ・ｓのＳｉＨ基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）０．６３ｋｇ、（Ａ３）として１－エチニルシクロヘキサノール（ワッカーケミ社製、）６３．５ｇを攪拌機（井上製作所製　プラネタリーミキサー）で４０分間撹拌した。別途、（Ａ２）として白金触媒（ワッカーケミ社製）３０．４ｇとポリシロキサン（ａ１）として粘度１０００ｍＰａ・ｓのビニル基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）１．０５ｋｇをスリーワンモーター（新東科学社製）で３０分間撹拌して得られた混合物０．９８ｋｇを、上記混合物に添加し、さらに４０分間撹拌し、最後に５μｍのＰＰ（ポリプロピレン）フィルターでろ過し、接着剤の成分（Ａ）を得た。 Preparation of Component (A) of Adhesive 22.49 kg of a base polymer (manufactured by Wacker Kemi Co., Ltd.) consisting of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa · s and a vinyl group-containing MQ resin as the polysiloxane (a1) 1.46 kg of SiH group-containing linear polydimethylsiloxane (made by Wacker Kemi) with a viscosity of 70 mPa · s as polysiloxane (a2), SiH group-containing linear polydimethylsiloxane with a viscosity of 100 mPa · s as polysiloxane (a2) 0.63 kg of Wacker Kemi Co., Ltd. and 63.5 g of 1-ethynylcyclohexanol (Wacker Kemi Co., Ltd.) as (A3) were stirred for 40 minutes with a stirrer (planetary mixer manufactured by Inoue Seisakusho Co., Ltd.). Separately, 30.4 g of a platinum catalyst (manufactured by Wacker Kemi) as (A2) and 1.05 kg of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Kemi) having a viscosity of 1000 mPa · s as polysiloxane (a1) as a three-one motor (newly 0.98 kg of the mixture obtained by stirring for 30 minutes with Higashi Scientific Co., Ltd. is added to the above mixture, stirred for additional 40 minutes, and finally filtered through a 5 μm PP (polypropylene) filter, and the components of the adhesive ( I got A).
（接着剤１）
成分（Ａ）ポリオルガノシロキサン９９質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）１質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１）を作製した。
Figure JPOXMLDOC01-appb-C000001
 式(Ｂ－１)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 1)
Component (A) 99% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., A mixture of 1 mass% (the ratio of the (A) component and the (B-1) component in the (B-1) component) under the trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 1).
Figure JPOXMLDOC01-appb-C000001
 In the formula (B-1), m and n indicate the number of repeating units.
（接着剤２）
成分（Ａ）ポリオルガノシロキサン９７．５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）２．５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤２）を作製した。 (Adhesive 2)
Component (A) 97.5% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (Gelest, Inc. Manufactured by trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s) 2.5 mass% (proportion of (A) component and (B-1) component in (B-1) component) The resulting mixture was mixed for 5 minutes with an autorotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: ARE-500) to prepare (adhesive 2).
（接着剤３）
成分（Ａ）ポリオルガノシロキサン９５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤３）を作製した。 (Adhesive 3)
Component (A) 95% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., A mixture of 5 mass% (the ratio of the component (A) to the component (B-1) in the component (B-1)) under the trade name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 3).
（接着剤４）
成分（Ａ）ポリオルガノシロキサン９０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）１０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤４）を作製した。 (Adhesive 4)
Component (A) 90% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 10% by mass (ratio of component (A) and component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd., brand name ARE-500), and produced (adhesive 4).
（接着剤５）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤５）を作製した。 (Adhesive 5)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 15% by mass (ratio of component (A) to component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 5).
（接着剤６）
成分（Ａ）ポリオルガノシロキサン７０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）３０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤６）を作製した。 (Adhesive 6)
Component (A) 70% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 30% by mass (ratio of component (A) to component (B-1) in component (B-1)) -It mixed for 5 minutes with the revolution mixer (made by Shinky Co., Ltd., brand name ARE-500), and produced (adhesive 6).
（接着剤７）
成分（Ａ）ポリオルガノシロキサン５０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）５０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤７）を作製した。 (Adhesive 7)
Component (A) 50% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s) 50% by mass (the ratio of the (A) component and the (B-1) component in the (B-1) component) -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 7).
（接着剤８）
成分（Ａ）ポリオルガノシロキサン３０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ａ）成分の割合）と、成分（Ｂ－１）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０４３、重量平均分子量６７０００、粘度３０，０００ｍｍ２／ｓ）７０質量％（（Ａ）成分と（Ｂ－１）成分中の（Ｂ－１）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤８）を作製した。 (Adhesive 8)
Component (A) 30% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-1)) and component (B-1) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1043, weight average molecular weight 67000, viscosity 30,000 mm 2 / s 70% by mass (ratio of component (A) and component (B-1) in component (B-1)) -It mixed for 5 minutes with a revolution mixer (made by Shinky Co., Ltd. make, brand name ARE-500), and produced (adhesive 8).
（接着剤９）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－２）成分中の（Ａ）成分の割合）と、成分（Ｂ－２）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＭＭ－１０２５、重量平均分子量２５２００、粘度５００ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－２）成分中の（Ｂ－２）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤９）を作製した。
Figure JPOXMLDOC01-appb-C000002
 式(Ｂ－２)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 9)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-2)) and component (B-2) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PMM-1025, weight average molecular weight 25200, viscosity 500mm 2 / s 15% by mass (ratio of (A) component and (B-2) component in (B-2) component) mixture of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 9).
Figure JPOXMLDOC01-appb-C000002
 In the formula (B-2), m and n indicate the number of repeating units.
（接着剤１０）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－３）成分中の（Ａ）成分の割合）と、成分（Ｂ－３）フェニル基変性シリコーン（信越化学工業株式会社製、商品名ＫＦ５０－３０００ＣＳ、重量平均分子量３９４００、粘度３０００ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－３）成分中の（Ｂ－３）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１０）を作製した。
Figure JPOXMLDOC01-appb-C000003
 式(Ｂ－３)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 10)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) and component (A)) and component (B-3) phenyl group-modified silicone (Shin-Etsu Chemical Co., Ltd.) KF 50-3000CS, weight average molecular weight 39,400, viscosity 3000 mm 2 / s) 15 mass% (ratio of component (A) to component (B-3) in component (B-3)) The mixture was mixed for 5 minutes with a revolution mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 10).
Figure JPOXMLDOC01-appb-C000003
 In the formula (B-3), m and n indicate the number of repeating units.
（接着剤１１）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－４）成分中の（Ａ）成分の割合）と、成分（Ｂ－４）フェニル基変性シリコーン（ＭＯＭＥＮＴＩＶＥ社製、商品名ＴＳＦ４３１、重量平均分子量１８００、粘度１００ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－４）成分中の（Ｂ－４）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１１）を作製した。
Figure JPOXMLDOC01-appb-C000004
 式(Ｂ－４)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 11)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-4)) and component (B-4) phenyl group-modified silicone (manufactured by MOMENTIVE, product name) A mixture consisting of TSF 431, weight average molecular weight 1800, viscosity 100 mm 2 / s, 15 mass% (proportion of (A) component and (B-4) component in (B-4) component) The mixture was mixed for 5 minutes under the trade name ARE-500, manufactured by Shinky Co., to prepare (adhesive 11).
Figure JPOXMLDOC01-appb-C000004
 In the formula (B-4), m and n indicate the number of repeating units.
（接着剤１２）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－５）成分中の（Ａ）成分の割合）と、成分（Ｂ－５）フェニル基変性シリコーン（ＭＯＭＥＮＴＩＶＥ社製、商品名ＴＳＦ４３３、重量平均分子量３０００、粘度４５０ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－５）成分中の（Ｂ－５）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１２）を作製した。
Figure JPOXMLDOC01-appb-C000005
 式(Ｂ－５)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 12)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-5)) and component (B-5) phenyl group-modified silicone (manufactured by MOMENTIVE, product name) A mixture consisting of TSF 433 (weight average molecular weight 3000, viscosity 450 mm 2 / s) 15 mass% (proportion of (A) component and (B-5) component in (B-5) component) Adhesive (Adhesive 12) was prepared by mixing for 5 minutes under the trade name ARE-500, manufactured by Shinky.
Figure JPOXMLDOC01-appb-C000005
 In the formula (B-5), m and n represent the number of repeating units.
（接着剤１３）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－６）成分中の（Ａ）成分の割合）と、成分（Ｂ－６）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＤＭ－０４２１、重量平均分子量６２００、粘度１００ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－６）成分中の（Ｂ－６）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１３）を作製した。
Figure JPOXMLDOC01-appb-C000006
 式(Ｂ－６)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 13)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-6)) and component (B-6) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PDM-0421, weight average molecular weight 6200, viscosity 100 mm 2 / s 15% by mass (ratio of (A) component and (B-6) component in (B-6) component) a mixture consisting of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 13).
Figure JPOXMLDOC01-appb-C000006
 In formula (B-6), m and n each represent the number of repeating units.
（接着剤１４）
成分（Ａ）ポリオルガノシロキサン８５質量％（（Ａ）成分と（Ｂ－７）成分中の（Ａ）成分の割合）と、成分（Ｂ－７）フェニル基変性シリコーン（Ｇｅｌｅｓｔ，Ｉｎｃ．製、商品名ＰＤＭ－０８２１、重量平均分子量８６００、粘度１２５ｍｍ２／ｓ）１５質量％（（Ａ）成分と（Ｂ－７）成分中の（Ｂ－７）成分の割合）からなる混合物を自転・公転ミキサー（株式会社シンキー製、商品名ＡＲＥ－５００）にて５分間混合し（接着剤１４）を作製した。
Figure JPOXMLDOC01-appb-C000007
 式(Ｂ－７)中、ｍ及びｎは繰り返し単位の数を示す。 (Adhesive 14)
Component (A) 85% by mass of polyorganosiloxane (ratio of component (A) to component (A) in component (B-7)) and component (B-7) phenyl group-modified silicone (manufactured by Gelest, Inc., Product name PDM-0821, weight average molecular weight 8600, viscosity 125 mm 2 / s 15% by mass (ratio of (A) component and (B-7) component in (B-7) component) a mixture consisting of rotation and revolution The mixture was mixed for 5 minutes with a mixer (trade name: ARE-500, manufactured by Shinky Co., Ltd.) to prepare (adhesive 14).
Figure JPOXMLDOC01-appb-C000007
 In the formula (B-7), m and n represent the number of repeating units.
（実施例１）
デバイス側のウエハーとして３００ｍｍのシリコーンウエハー（厚さ：７７０μｍ）に、仮接着層を形成させるためにスピンコートにて上記接着剤（１）～（８）をそれぞれ約５０μｍの膜厚でウエハーの回路面に成膜し、それぞれの接着層（１）～（８）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍガラスウエハー（厚さ：７００μｍ）を、上記接着層を挟むように真空貼り合せ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合せ、積層体を作製した。 Example 1
As a wafer on the device side, a 300 mm silicone wafer (thickness: 770 μm), and the above adhesive (1) to (8) by spin coating to form a temporary adhesive layer, each having a film thickness of about 50 μm. A film was formed on the surface to form the adhesive layers (1) to (8). A vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 μm) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck inside and produced the layered product.
その後、ホットプレート上で２００℃で１０分間の加熱処理を行った。その後、ボイドの有無をガラスウエハー（支持体）側から確認した。接着性として加熱処理後にボイドが見られなかったもの良好として「○」、見られたものを不良として「×」と表記した。続いて貼り合わせしたウエハーを、減圧度１３Paのオーブンで２２０℃で１０分間加熱処理を行った。その後、ボイドの有無をガラスウエハー（支持体）側から確認した。耐熱性として加熱処理後にボイドが見られなかったものを良好として「○」、みられたものを不良として「×」と表記した。また剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にて剥離に要する力を測定した。剥離ができたものに関しては、良好な結果として剥離に要した力を数値で示し、剥離ができなかったものに関しては不良として「×」と表記した。また剥離性の確認の際、剥離界面を確認した。剥離がデバイス側ウエハーと接着層との界面で生じ、良好に制御できている場合は「デバイス」、キャリア側ウエハー（支持体）と接着層との界面で生じ、良好に制御できている場合は「キャリア」、剥離界面が「デバイス」側とも「キャリア」側とも言えない場合は「△」、接着層にて凝集破壊を起こしたものを「×」、剥離できなかったものを「－」と表記した。結果を表1に示す。
〔表１〕
　　　　　　　　　　　　表１（実施例１の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　接着性        耐熱性        剥離性        剥離界面
接着層（１）  　○          　○          　×          　　－
接着層（２）  　○          　○          　×          　　－
接着層（３）  　○          　○          ２６N         　キャリア
接着層（４）  　○          　○          ２３N         　キャリア
接着層（５）  　○          　○          ２０N         　キャリア
接着層（６）  　○          　○          １９N         　キャリア
接着層（７）  　○          　○          ２０N         　キャリア
接着層（８）  　○          　○          ２０N         　キャリア
――――――――――――――――――――――――――――――――― Thereafter, heat treatment was performed at 200 ° C. for 10 minutes on a hot plate. Thereafter, the presence or absence of a void was confirmed from the glass wafer (support) side. As adhesiveness, what was not able to see the void after heat processing as "good" was described as "good", and what was seen was described as "poor" as defect. Subsequently, the bonded wafer was subjected to heat treatment at 220 ° C. for 10 minutes in an oven with a degree of vacuum of 13 Pa. Thereafter, the presence or absence of a void was confirmed from the glass wafer (support) side. As heat resistance, the thing in which the void was not seen after heat processing was noted as "good" as "good", and what was seen as poor as "x". Moreover, in order to confirm peelability, the force required for peeling was measured with a peeling apparatus (made by SUSS Microtech, manual debonder). For those that were able to be peeled off, the force required for peeling was shown numerically as a good result, and for those that could not be peeled off, it was marked as "x" as a defect. Moreover, in the case of confirmation of peelability, the peeling interface was confirmed. Peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled. If it can not be said that "carrier" and the peeling interface are both "device" and "carrier", "△", those that caused cohesive failure in the adhesive layer are "X", and those that could not be peeled are "-" I wrote it. The results are shown in Table 1.
[Table 1]
Table 1 (Result of Example 1)
――――――――――――――――――――――――――――――――――――
Adhesiveness Heat resistance Peelability Peeling interface adhesive layer (1) ○ ○ ×-
Adhesive layer (2) ○ ○ ×-
Adhesive layer (3) ○ ○ 26N carrier adhesive layer (4) ○ ○ 23N carrier adhesive layer (5) ○ ○ 20N carrier adhesive layer (6) ○ ○ 19N carrier adhesive layer (7) ○ ○ 20N carrier adhesive layer (8) ○ ○ 20N Carrier ――――――――――――――――――――――――――――――――
表１の結果から、接着層（１）、（２）では接着性および耐熱性は良好な結果であるが、剥離性については良好な結果が得られなかった。一方で接着層（３）～（８）について、接着性、耐熱性、剥離性、剥離界面の制御において良好な結果が得られた。 From the results of Table 1, in the adhesive layers (1) and (2), the adhesion and the heat resistance are good results, but the peelability was not good. On the other hand, for the adhesive layers (3) to (8), good results were obtained in control of adhesiveness, heat resistance, peelability, and peel interface.
（実施例２）
デバイス側のウエハーとして３００ｍｍのシリコーンウエハー（厚さ：７７０μｍ）に、仮接着層を形成させるためにスピンコートにて上記接着剤（５）を約５０μｍの膜厚で三つウエハーの回路面に成膜し、それぞれ接着層（５－１）～（５－３）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍガラスウエハー（厚さ：７００μｍ）を、上記接着層を挟むように真空貼り合せ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合せ、積層体を作製した。その後、ホットプレート上で２００℃で１０分間の加熱処理を行った。この際、デバイス側ウエハーを下にして加熱処理したものを「デバイス」と表記し、キャリア側ウエハー（支持体）を下にして加熱処理したものを「キャリア」と表記した。また加熱処理をイナートガスオーブン（エスペック社製）を使用して２００℃で１０分間行ったものを「オーブン」と表記した。 (Example 2)
As a wafer on the device side, a 300 mm silicone wafer (thickness: 770 μm) was spin coated to form the above adhesive (5) with a film thickness of about 50 μm on the circuit surface of three wafers to form a temporary adhesive layer. The films were formed into adhesive layers (5-1) to (5-3), respectively. A vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 μm) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck inside and produced the layered product. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes on a hot plate. Under the present circumstances, what heat-processed with the device side wafer down was described as "device", and what heat-processed the carrier side wafer (support body) down was described as "carrier." Moreover, what performed heat processing for 10 minutes at 200 degreeC using inert gas oven (made by Espec) was described as "oven."
さらに剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にて剥離に要する力を測定した。剥離ができたものに関しては、良好な結果として剥離に要した力を数値で示し、剥離ができなかったものに関しては不良として「×」と表記した。また剥離性の確認の際、剥離界面を確認した。剥離がデバイス側ウエハーと接着層との界面で生じ、良好に制御できている場合は「デバイス」、キャリア側ウエハー（支持体）と接着層との界面で生じ、良好に制御できている場合は「キャリア」、剥離できなかったものを不良として「×」とした。結果を表２に示す。
〔表２〕
　　　　　　　　　　　　表２（実施例２の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　　　　加熱処理面           剥離性        剥離界面
接着層（５－１）     デバイス             ２０N         キャリア
接着層（５－２）     キャリア             １７N         キャリア
接着層（５－３）     オーブン             １８N         キャリア
――――――――――――――――――――――――――――――――― Furthermore, in order to confirm peelability, the force required for peeling was measured with a peeling apparatus (made by SUSS Microtech, manual debonder). For those that were able to be peeled off, the force required for peeling was shown numerically as a good result, and for those that could not be peeled off, it was marked as "x" as a defect. Moreover, in the case of confirmation of peelability, the peeling interface was confirmed. Peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled. The "carrier" and the one that could not be peeled off was regarded as "poor". The results are shown in Table 2.
[Table 2]
Table 2 (Result of Example 2)
――――――――――――――――――――――――――――――――――――
Heat treated surface Peelable Peelable interface adhesive layer (5-1) Device 20N Carrier adhesive layer (5-2) Carrier 17N Carrier adhesive layer (5-3) Oven 18N carrier------------ ――――――――――――――――――――――――
表２の結果では、接着剤（５）から形成された接着層（５－１）～（５－３）では、剥離性において良好な結果を示した。また接着剤の硬化時に行う加熱処理方法により剥離界面は変化せず、キャリアと接着剤の界面で剥離可能であることが確認された。 In the results of Table 2, the adhesive layers (5-1) to (5-3) formed of the adhesive (5) showed good results in terms of peelability. Further, it was confirmed that the peeling interface was not changed by the heat treatment method performed at the time of curing of the adhesive, and that peeling was possible at the interface of the carrier and the adhesive.
（実施例３）
デバイス側のウエハーとして３００ｍｍのシリコンウエハー（厚さ：７７０μｍ）に、仮接着層を形成するためにスピンコートにて上記接着剤（５）を約１００μｍの膜厚でウエハーの回路面に成膜し、接着層（５－７）とした。この接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍガラスウエハー（厚さ：７００μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。その後、ホットプレート上でデバイス側ウエハーが下となるように２００℃で１０分間、加熱処理を実施した。 (Example 3)
The above adhesive (5) is formed on the circuit surface of the wafer with a film thickness of about 100 μm by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 μm) as a wafer on the device side. , Adhesive layer (5-7). A wafer having this adhesive layer and a 300 mm glass wafer (thickness: 700 μm) as a wafer on the carrier side (support) in a vacuum bonding apparatus (manual bonder, manufactured by SUSS MicroTec) so as to sandwich the adhesive layer. The laminates were produced in the following manner. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes so that the device-side wafer was on the hot plate.
その後、剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にて剥離に要する力を測定した。剥離ができたものに関しては、良好な結果として剥離に要した力を数値で示し、剥離ができなかったものに関しては不良として「×」と表記した。また剥離性の確認の際、剥離界面を確認した。剥離がデバイス側ウエハーと接着層との界面で生じ、良好に制御できている場合は「デバイス」、キャリア側ウエハー（支持体）と接着層との界面で生じ、良好に制御できている場合は「キャリア」、剥離できなかったものを不良として「×」と表記した。結果を表３に示す。
〔表３〕
　　　　　　　　　　　　表３（実施例３の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　    仮接着層の膜厚       　剥離性  　　　 剥離界面
接着層（５－１）     ５０μｍ      　　　２０N          キャリア
接着層（５－７）     １００μｍ    　　　２３N          キャリア
――――――――――――――――――――――――――――――――― Then, in order to confirm peelability, the force required for peeling was measured with a peeling apparatus (made by SUSS Microtech, manual debonder). For those that were able to be peeled off, the force required for peeling was shown numerically as a good result, and for those that could not be peeled off, it was marked as "x" as a defect. Moreover, in the case of confirmation of peelability, the peeling interface was confirmed. Peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled. The "carrier" and the one that could not be peeled off was described as "x" as a defect. The results are shown in Table 3.
[Table 3]
Table 3 (Result of Example 3)
――――――――――――――――――――――――――――――――――――
Thickness of temporary adhesive layer Peelability Peeling interface adhesive layer (5-1) 50μm 20N Carrier adhesive layer (5-7) 100μm 23N carrier----------------- ――――――――――――――――
表３の結果から、接着剤（５）により形成された接着層（５－７）では、接着層の膜厚によらず剥離性は良好であることを示した。 From the results in Table 3, it was shown that in the adhesive layer (5-7) formed by the adhesive (5), the releasability was good regardless of the thickness of the adhesive layer.
(実施例４)
デバイス側のウエハーとして３００ｍｍのシリコンウエハー（厚さ：７７０μｍ）に、仮接着層を形成するためにスピンコートにて上記接着剤（５）を約５０μｍの膜厚で四つのウエハーの回路面に成膜し、それぞれ接着層（５－８）～（５－１１）とした。この接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍガラスウエハー（厚さ：７００μｍ）で上記接着剤層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。その後、ホットプレート上でデバイス側ウエハーが下となるようにそれぞれ１２０℃、１５０℃、２２０℃、２６０℃で１０分間、加熱処理を実施した。 (Example 4)
The above adhesive (5) is formed on the circuit surface of four wafers with a film thickness of about 50 μm by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 μm) as a wafer on the device side. The membranes were formed into adhesive layers (5-8) to (5-11), respectively. In a vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the above adhesive layer is sandwiched between a wafer having this adhesive layer and a 300 mm glass wafer (thickness: 700 μm) as a wafer on the carrier side (support) The laminates were produced in the following manner. After that, heat treatment was performed at 120 ° C., 150 ° C., 220 ° C., and 260 ° C. for 10 minutes so that the device-side wafer was on the hot plate.
その後、剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にて剥離に要する力を測定した。剥離ができたものに関しては、良好な結果として剥離に要した力を数値で示し、剥離ができなかったものに関しては不良として「×」と表記した。また剥離性の確認の際、剥離界面を確認した。剥離がデバイス側ウエハーと接着層との界面で生じ、良好に制御できている場合は「デバイス」、キャリア側ウエハー（支持体）と接着層との界面で生じ、良好に制御できている場合は「キャリア」、剥離できなかったものを不良として「×」と表記した。結果を表４に示す。
〔表４〕
　　　　　　　　　　　　表４（実施例４の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　　　　加熱処理温度　　　 　剥離性　　　　剥離界面
接着層（５－８）     １２０℃      　　　１７N   　　　キャリア
接着層（５－９）     １５０℃      　　　１７N   　　　キャリア
接着層（５－１０）   ２２０℃      　　　１８N   　　　キャリア
接着層（５－１１）   ２６０℃      　　　２１N   　　　キャリア
――――――――――――――――――――――――――――――――― Then, in order to confirm peelability, the force required for peeling was measured with a peeling apparatus (made by SUSS Microtech, manual debonder). For those that were able to be peeled off, the force required for peeling was shown numerically as a good result, and for those that could not be peeled off, it was marked as "x" as a defect. Moreover, in the case of confirmation of peelability, the peeling interface was confirmed. Peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled. The "carrier" and the one that could not be peeled off was described as "x" as a defect. The results are shown in Table 4.
[Table 4]
Table 4 (Result of Example 4)
――――――――――――――――――――――――――――――――――――
Heat treatment temperature Peelability Peelable interface adhesive layer (5-8) 120 ° C 17N Carrier adhesive layer (5-9) 150 ° C 17N Carrier adhesive layer (5-10) 220 ° C 18N Carrier adhesive layer (5-11) 260 ° C 21N Career---------------------------
表４の結果から、接着剤（５）により形成された接着層（５－８）～（５－１１）では、加熱処理温度によらず剥離性は良好であることを示した。 From the results of Table 4, it was shown that in the adhesive layers (5-8) to (5-11) formed by the adhesive (5), the releasability was good regardless of the heat treatment temperature.
（実施例５）
デバイス側のウエハーとして３００ｍｍのシリコンウエハー（厚さ：７７０μｍ）に、仮接着層を形成するためにスピンコートにてそれぞれ上記接着剤（５）、（９）～（１４）を約５０μｍの膜厚でウエハーの回路面に成膜し、それぞれ接着層（５－１２）、（９）～（１４）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍガラスウエハー（厚さ：７００μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。 (Example 5)
The above adhesive (5) and (9) to (14) with a thickness of about 50 μm are formed by spin coating to form a temporary adhesive layer on a 300 mm silicon wafer (thickness: 770 μm) as a wafer on the device side. The films were formed on the circuit surface of the wafer as adhesion layers (5-12) and (9) to (14), respectively. A vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so as to sandwich the adhesive layer between the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 700 μm) as a wafer on the carrier side (support) It stuck together inside and produced the layered product.
その後、ホットプレート上でデバイス側ウエハーを下にして２００℃で１０分間、加熱処理を行った。その後、ボイドの有無をガラスウエハー側から確認した。接着性として加熱処理後にボイドが見られなかったもの良好として「○」、見られたものを不良として「×」と表記した。また剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にて剥離に要する力を測定した。剥離ができたものに関しては、良好な結果として剥離に要した力を数値で示し、剥離ができなかったものに関しては不良として「×」と表記した。また剥離性の確認の際、剥離界面を確認した。剥離がデバイス側ウエハーと接着層との界面で生じ、良好に制御できている場合は「デバイス」、キャリア側ウエハー（支持体）と接着層との界面で生じ、良好に制御できている場合は「キャリア」、剥離界面が「デバイス」側とも「キャリア」側とも言えない場合は「△」、接着層にて凝集破壊を起こしたものを「×」、剥離できなかったものを「‐」と表記した。結果を表５に示す。
〔表５〕
　　　　　　　　　　　　表５（実施例５の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　    接着性　　　　耐熱性　　  剥離性　　　剥離界面
接着層（５－１２）   ○     　　　○      　２０Ｎ      キャリア
接着層（９）         ○     　　　○      　３２Ｎ      キャリア
接着層（１０）       ○     　　　○      　３０Ｎ      キャリア
接着層（１１）       ○     　　　○      　　×        　－
接着層（１２）       ○     　　　○      　　×        　－
接着層（１３）       ○     　　　○      　　×        　－
接着層（１４）       ○     　　　○      　　×        　－
――――――――――――――――――――――――――――――――― After that, heat treatment was performed at 200 ° C. for 10 minutes with the device-side wafer down on the hot plate. Then, the presence or absence of a void was confirmed from the glass wafer side. As adhesiveness, what was not able to see the void after heat processing as "good" was described as "good", and what was seen was described as "poor" as defect. Moreover, in order to confirm peelability, the force required for peeling was measured with a peeling apparatus (made by SUSS Microtech, manual debonder). For those that were able to be peeled off, the force required for peeling was shown numerically as a good result, and for those that could not be peeled off, it was marked as "x" as a defect. Moreover, in the case of confirmation of peelability, the peeling interface was confirmed. Peeling occurs at the interface between the wafer on the device side and the adhesive layer, and when it is well controlled, it occurs at the interface between the wafer on the carrier side (support) and the adhesive layer, and when it is well controlled. When the peeling interface is neither "device" nor "carrier" side, "」 "indicates that the cohesive failure occurred in the adhesive layer is" X ", and if it can not be peeled"-" I wrote it. The results are shown in Table 5.
[Table 5]
Table 5 (Result of Example 5)
――――――――――――――――――――――――――――――――――――
Adhesive heat resistance Peelable Peeling interface adhesive layer (5-12) ○ ○ 20N Carrier adhesive layer (9) ○ ○ 32N Carrier adhesive layer (10) ○ ○ 30N Carrier adhesive layer (11) ○ ○ ×-
Adhesive layer (12) ○ ○ ×-
Adhesive layer (13) ○ ○ ×-
Adhesive layer (14) ○ ○ ×-
――――――――――――――――――――――――――――――――――――
表５の結果から、接着剤（５）により形成された接着層（５－１２）、そして接着層（９）、接着層（１０）では、接着性、剥離性は良好であることを示した。 From the results of Table 5, it was shown that the adhesive properties and the releasability of the adhesive layer (5-12) formed by the adhesive (5), and the adhesive layer (9) and the adhesive layer (10) were good. .
（実施例６）
デバイス側のウエハーとして３００ｍｍのトリムシリコンウエハー（厚さ：７７０μｍ）に、仮接着層を形成するためにスピンコートにて上記の接着剤（５）を約５０μｍの膜厚でウエハーの回路面に成膜し、接着層（５－１３）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍのシリコンウエハー（厚さ：７７０μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。 (Example 6)
The above adhesive (5) is formed on the circuit surface of the wafer with a film thickness of about 50 μm by spin coating to form a temporary adhesive layer on a trimmed silicon wafer (thickness: 770 μm) of 300 mm as a wafer on the device side. The membrane was formed into an adhesive layer (5-13). A vacuum bonding device (manual bonder, manufactured by Suse Microtech, Inc., so that the above-mentioned adhesive layer is sandwiched between the wafer having the adhesive layer and a 300 mm silicon wafer (thickness: 770 μm) as a wafer (support) on the carrier side. ) Pasted together to make a laminate.
その後、ホットプレート上でデバイス側ウエハーを下にして２００℃で１０分間、加熱処理を行った。その後、裏面研削装置（東京精密社製、バックグラインダー）でデバイス側ウエハーの薄化処理を実施した。薄化処理後のデバイス側ウエハーのエッジを光学顕微鏡で観察し、チッピングが無かったものを良好として「○」と表記し、チッピングが生じたものを「×」と表記した。結果を表６に示す。
〔表６〕
　　　　　　　　　　　　表６（実施例６の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　　　　　　　　チッピング
接着層（５－１３）          　　○
――――――――――――――――――――――――――――――――― After that, heat treatment was performed at 200 ° C. for 10 minutes with the device-side wafer down on the hot plate. Thereafter, the wafer on the device side was thinned with a back grinding device (back grinder, manufactured by Tokyo Seimitsu Co., Ltd.). The edge of the device-side wafer after the thinning treatment was observed with an optical microscope, and those without chipping were regarded as good as “○”, and those with chipping as “×”. The results are shown in Table 6.
[Table 6]
Table 6 (Result of Example 6)
――――――――――――――――――――――――――――――――――――
Chipping adhesive layer (5-13) ○
――――――――――――――――――――――――――――――――――――
表６の結果から、接着剤（５）により形成された接着層（５－１３）では、デバイス側ウエハーの薄化処理工程においてチッピングは確認されず、良好な結果であることを示した。 From the results of Table 6, in the adhesive layer (5-13) formed by the adhesive (5), chipping was not confirmed in the thinning treatment process of the device-side wafer, and it was shown that the result was a good result.
（実施例７）デバイスウエハーの洗浄試験
デバイス側のウエハーとしてグローバルネット株式会社製３００ｍｍＰＩウエハー（厚さ：７７０μｍ、下地：ＳｉＮ＋ＰＩ、スクライブライン：幅１００ｍｍ、１５ｍｍピッチ）に、仮接着層を形成するためにスピンコートにて上記接着剤（５）を約５０μｍの膜厚でウエハーの回路面に成膜し、接着層（５－１４）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍのガラスウエハー（厚さ：７７０μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。 Example 7 Cleaning Test of Device Wafer As a wafer on the testing side of the device wafer, a temporary adhesive layer is formed on a global net 300 mm PI wafer (thickness: 770 μm, base: SiN + PI, scribe line: width 100 mm, 15 mm pitch) The adhesive (5) was formed on the circuit surface of the wafer with a thickness of about 50 μm by spin coating to form an adhesive layer (5-14). A vacuum bonding device (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 μm) as a wafer (support) on the carrier side sandwich the adhesive layer. ) Pasted together to make a laminate.
その後、ホットプレート上でデバイス側ウエハーを下にして２００℃で１０分間、加熱処理を行った。また剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にてデバイス側ウエハーと接着層（５－１４）との間で剥離を実施した。この際、大部分の接着層はキャリア側に残存しているが、デバイス側ウエハーに極わずかに残存している接着剤を除去するために、テトラブチルアンモニウムフルオリド、DBU（ジアザビシクロウンデセン）、及び２－ヘプタノンからなるクリーナーで１０分間、パドル洗浄を実施した。その後、光学顕微鏡にて表面を観察し、完全に接着剤が除去できている場合を良好と評価し「○」で示し、除去できなかったものを「×」で表記した。結果を表７に示す。
〔表７〕
　　　　　　　　　　　　表７（実施例７の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　　　　　　　　洗浄試験
接着層（５－１４）           　○
――――――――――――――――――――――――――――――――― After that, heat treatment was performed at 200 ° C. for 10 minutes with the device-side wafer down on the hot plate. Further, in order to confirm the releasability, separation was carried out between the device-side wafer and the adhesive layer (5-14) with a separation device (manual debonder manufactured by SUSS Microtech, Inc.). At this time, most of the adhesive layer remains on the carrier side, but tetrabutyl ammonium fluoride, DBU (diazabicycloundecene) is used to remove the adhesive that is only slightly left on the device side wafer. The paddle was cleaned for 10 minutes with a cleaner consisting of 2) and 2-heptanone. Thereafter, the surface was observed with an optical microscope, and the case where the adhesive was completely removed was evaluated as good, indicated by “o”, and those that could not be removed were indicated by “x”. The results are shown in Table 7.
[Table 7]
Table 7 (Result of Example 7)
――――――――――――――――――――――――――――――――――――
Cleaning test adhesion layer (5-14) ○
――――――――――――――――――――――――――――――――――――
表７の結果から、接着剤（５）により形成された接着層（５－１４）では、上記クリーナーを用いたパドル洗浄により、デバイス側のウエハー表面が完全に洗浄され良好であることを示した。 From the results of Table 7, it was shown that the wafer surface on the device side was completely cleaned and good in the adhesive layer (5-14) formed by the adhesive (5) by the paddle cleaning using the above-mentioned cleaner .
（実施例８）テープによるリフトオフ
デバイス側のウエハーとしてグローバルネット株式会社製３００ｍｍＰＩウエハー（厚さ：７７０μｍ、下地：ＳｉＮ＋ＰＩ、スクライブライン：幅１００ｍｍ、１５ｍｍピッチ）に、仮接着層を形成するためにスピンコートにて上記の接着剤（５）を約５０μｍの膜厚でウエハーの回路面に成膜し、接着層（５－１５）とした。ここの接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍのガラスウエハー（厚さ：７７０μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。 (Example 8) As a wafer on the lift-off device side by tape, spin is used to form a temporary adhesive layer on 300 mm PI wafer (thickness: 770 μm, base: SiN + PI, scribe line: width 100 mm, 15 mm pitch) The above adhesive (5) was formed into a film of about 50 μm thick on the circuit surface of the wafer by coating to form an adhesive layer (5-15). A vacuum bonding device (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 μm) as a wafer (support) on the carrier side sandwich the adhesive layer. ) Pasted together to make a laminate.
その後、ホットプレート上でデバイス側ウエハーを下にして２００℃で１０分間、加熱処理を行った。また剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にてデバイス側ウエハーと接着層（５－１５）との界面で剥離を実施した。 After that, heat treatment was performed at 200 ° C. for 10 minutes with the device-side wafer down on the hot plate. Further, in order to confirm the releasability, separation was performed at the interface between the device-side wafer and the adhesive layer (5-15) with a separation device (manual debonder manufactured by SUSS MicroTec).
一方、比較として成分（Ａ）のみからなる接着剤を約５０μｍの膜厚で、キャリア側のウエハー（支持体）として３００ｍｍのガラスウエハー（厚さ：７７０μｍ）に塗布し、接着層（Ａ－１）とした。その後２００℃で１０分間、加熱処理を行った。 On the other hand, for comparison, an adhesive consisting only of the component (A) is applied to a thickness of about 50 μm to a 300 mm glass wafer (thickness: 770 μm) as a wafer on the carrier side (support), adhesive layer (A-1) ). Then, heat treatment was performed at 200 ° C. for 10 minutes.
その後、キャリア側ウエハー（支持体）に残存した接着層（５－１５）及び（Ａ－１）に対して、プリント基板めっき時の端子部マスキング用テープ（日東電工株式会社製、商品名Ｎ‐３００）を用いてそれぞれテープピーリング法により接着剤の剥離試験を行った。上記テープをキャリア側ウエハー（支持体）の接着剤表面に貼り付け、キャリア側ウエハー（支持体）に対して６０～１８０°の範囲の角度でテープを引きはがし、キャリア側のウエハー（支持体）から接着層（５－１５）及び（Ａ－１）を分離する試験を行った。 Thereafter, with respect to the adhesive layers (5-15) and (A-1) remaining on the carrier side wafer (support), a terminal masking tape (made by Nitto Denko Corporation, trade name N-) at the time of printed circuit board plating. The peeling test of the adhesive was carried out by the tape peeling method using 300). Attach the above tape to the adhesive surface of the carrier side wafer (support), peel off the tape from the carrier side wafer (support) at an angle in the range of 60 to 180 °, and the carrier side wafer (support) A test was conducted to separate the adhesive layers (5-15) and (A-1) from
分離できた場合を良好と評価し「○」で示し、できなかったものを「×」で示した。
〔表８〕
　　　　　　　　　　　　表８（実施例８の結果）
―――――――――――――――――――――――――――――――――
　　　　　　　　　　　　　　テープピーリング試験
接着層（５－１５）          　     　○
接着層（Ａ－１）                   　×
――――――――――――――――――――――――――――――――― The case where separation was possible was evaluated as good and indicated by “o”, and those that could not be indicated by “x”.
[Table 8]
Table 8 (Results of Example 8)
――――――――――――――――――――――――――――――――――――
Tape peeling test adhesive layer (5-15) ○
Adhesive layer (A-1) ×
――――――――――――――――――――――――――――――――――――
表８の結果から、接着剤（５）により形成された接着層（５－１５）では、上記テープによるリフトオフ工程で接着層が除去され、良好な結果であることを示した。一方で、比較例として挙げた成分（Ａ）により形成された接着層（Ａ－１）においてはリフトオフ工程での接着層の除去が確認されなかった。 The results shown in Table 8 indicate that the adhesive layer (5-15) formed by the adhesive (5) was removed in the lift-off step using the above-mentioned tape, which is a good result. On the other hand, in the adhesive layer (A-1) formed of the component (A) mentioned as the comparative example, removal of the adhesive layer in the lift-off process was not confirmed.
（実施例９）キャリアウエハー（支持体）の溶剤による再生試験
デバイス側のウエハーとしてグローバルネット株式会社製３００ｍｍＰＩウエハー（厚さ：７７０μｍ、下地：ＳｉＮ＋ＰＩ、スクライブライン：幅１００ｍｍ、１５ｍｍピッチ）に、仮接着層を形成するためにスピンコートにて上記接着剤（５）を約５０μｍの膜厚でウエハーの回路面に成膜し、接着層（５－１６）とした。この接着層を有するウエハーと、キャリア側のウエハー（支持体）として３００ｍｍのガラスウエハー（厚さ：７７０μｍ）を、上記接着層を挟むように真空貼り合わせ装置（ズースマイクロテック社製、マニュアルボンダー）内で貼り合わせ、積層体を作製した。 (Example 9) Regeneration test of carrier wafer (support) with solvent As a wafer on the test device side of 300 nm PI wafer (thickness: 770 μm, base: SiN + PI, scribe line: width 100 mm, pitch 15 mm) manufactured by Globalnet Inc. In order to form an adhesive layer, the above-mentioned adhesive (5) was formed on the circuit surface of the wafer with a film thickness of about 50 μm by spin coating to form an adhesive layer (5-16). A vacuum bonding apparatus (manual bonder, manufactured by Suse Microtech Co., Ltd.) so that the wafer having the adhesive layer and a 300 mm glass wafer (thickness: 770 μm) as a wafer (support) on the carrier side sandwich the adhesive layer. It stuck together inside and produced the layered product.
その後、ホットプレート上でデバイス側ウエハーを下にして２００℃で１０分間、加熱処理を行った。また剥離性を確認するために剥離装置（ズースマイクロテック社製、マニュアルデボンダー）にてデバイス側ウエハーと接着層（５－１６）との界面で剥離を実施した。 After that, heat treatment was performed at 200 ° C. for 10 minutes with the device-side wafer down on the hot plate. Further, in order to confirm the releasability, the separation was performed at the interface between the device-side wafer and the adhesive layer (5-16) with a separation device (manual debonder manufactured by SUSS Microtech, Inc.).
一方、比較として成分（Ａ）のみからなる接着剤を約５０μｍの膜厚で、キャリア側のウエハー（支持体）として３００ｍｍのガラスウエハー（厚さ：７７０μｍ）に塗布し、接着層（Ａ－２）とした。その後２００℃で１０分間、加熱処理を行った。 On the other hand, for comparison, an adhesive consisting only of the component (A) is applied to a thickness of about 50 μm to a 300 mm glass wafer (thickness: 770 μm) as a wafer on the carrier side (support), adhesive layer (A-2) ). Then, heat treatment was performed at 200 ° C. for 10 minutes.
その後、キャリア側ウエハー（支持体）に残存した接着層（５－１６）、及び（Ａ－２）をＩｓｏｐｅｒ‐Ｅ（安藤パラケミー株式会社製、炭化水素系溶剤）及びシェルゾールＭＣ４２１（シェルケミカルズジャパン株式会社製、炭化水素系溶剤）に浸漬させ、溶剤による接着層の除去を実施した。溶剤浸漬後に接着層がリフトオフによる除去ができた場合を良好と評価し「○」で示し、リフトオフによる除去ができなかった場合を「×」で示した。
〔表９〕
　　　　　　　　　　　　表９（実施例９の結果）
―――――――――――――――――――――――――――――――――
                     　Ｉｓｏｐｅｒ‐Ｅ   シェルゾールＭＣ４２１
接着層（５－１６）          　○                 ○
接着層（Ａ－２）            　×                 ×
――――――――――――――――――――――――――――――――― Thereafter, the adhesive layer (5-16) remaining on the wafer on the carrier side (support), and (A-2) are made of Isoper-E (hydrocarbon solvent manufactured by Ando Parachemy Co., Ltd.) and Shellsol MC421 (Shell Chemicals Japan) The resultant was immersed in a hydrocarbon-based solvent (manufactured by Kabushiki Kaisha, Ltd.) to remove the adhesive layer with the solvent. The case where the adhesion layer was able to be removed by lift-off after immersion in a solvent was evaluated as good and indicated by “o”, and the case where removal by lift-off was not possible was indicated by “x”.
[Table 9]
Table 9 (Results of Example 9)
――――――――――――――――――――――――――――――――――――
Isoper-E Shersol MC421
Adhesive layer (5-16) ○ ○
Adhesive layer (A-2) × ×
――――――――――――――――――――――――――――――――――――
本発明にかかわる積層体は、添加剤として支持体（支持基板）とウエハーの間に仮接着層があり、その仮接着層を形成する接着剤はヒドロシリル化反応により硬化するポリオルガノシロキサン成分と、添加剤としてフェニル基含有ポリオルガノシロキサン成分とを含む接着剤を含むものである。これにより剥離層形成の必要がなく、ウエハー裏面の研磨後には容易に剥離が可能となる。
  The laminate according to the present invention has a temporary adhesive layer between the support (support substrate) and the wafer as an additive, and the adhesive forming the temporary adhesive layer is a polyorganosiloxane component cured by a hydrosilylation reaction, It contains an adhesive containing a phenyl group-containing polyorganosiloxane component as an additive. As a result, there is no need to form a peeling layer, and peeling can be easily performed after polishing the back surface of the wafer.

Claims (14)

  1. 支持体とウエハーの回路面との間で剥離可能に接着し、ウエハーの裏面を加工するための接着剤であり、前記接着剤がヒドロシリル化反応により硬化する成分（Ａ）と、フェニル基含有ポリオルガノシロキサンとを含む成分（Ｂ）とを含み、成分（Ａ）と成分（Ｂ）の質量％が９５：５～３０：７０の割合である前記接着剤。 An adhesive for releasably bonding between a support and a circuit surface of a wafer and processing the back surface of the wafer, wherein the adhesive cures by a hydrosilylation reaction (A), and a phenyl group-containing poly The above adhesive, which comprises a component (B) containing an organosiloxane, and the ratio by mass of the component (A) to the component (B) is 95: 5 to 30:70.
  2. 前記成分（Ａ）が、ＳｉＯ２で表されるシロキサン単位（Ｑ単位）、Ｒ１Ｒ２Ｒ３ＳｉＯ１／２で表されるシロキサン単位（Ｍ単位）、Ｒ４Ｒ５ＳｉＯ２／２で表されるシロキサン単位（Ｄ単位）、及びＲ６ＳｉＯ３／２で表されるシロキサン単位（Ｔ単位）からなる群より選ばれるポリシロキサン（但しＲ１乃至Ｒ６はそれぞれＳｉ－Ｃ結合又はＳｉ－Ｈ結合によりケイ素原子に結合しているものである。）を含み、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と炭素原子数２～１０のアルケニル基を含むポリオルガノシロキサン（ａ１）と、Ｒ１乃至Ｒ６で示される１価化学基がそれぞれ炭素原子数１～１０のアルキル基と水素原子を含むポリオルガノシロキサン（ａ２）とを含むポリシロキサン（Ａ１）と、白金族金属系触媒（Ａ２）とを含むものである請求項１に記載の接着剤。 Wherein component (A), siloxane units represented by SiO 2 (Q unit) siloxane units represented by R 1 R 2 R 3 SiO 1/2 (M units), in R 4 R 5 SiO 2/2 A polysiloxane selected from the group consisting of a siloxane unit (D unit) represented by the formula and a siloxane unit (T unit) represented by R 6 SiO 3/2 (with the proviso that R 1 to R 6 each represent a Si—C bond or Si by -H bond is one that is bonded to a silicon atom.), wherein the monovalent chemical group represented by R 1 to R 6 is an alkyl group and 2 to 10 carbon atoms of 1 to 10 carbon atoms, respectively A polyorganosiloxane comprising an alkenyl group-containing polyorganosiloxane (a1) and a polyorganosiloxane (a2) in which the monovalent chemical groups represented by R 1 to R 6 each contain an alkyl group having 1 to 10 carbon atoms and a hydrogen atom. The adhesive according to claim 1, which contains siloxane (A1) and a platinum group metal catalyst (A2).
  3. 前記成分 （Ｂ）が、（ｂ１）フェニルメチルシロキサン単位構造又はジフェニルシロキサン単位構造と、（ｂ２）ジメチルシロキサン単位構造との組み合わせである請求項１又は請求項２に記載の接着剤。 The adhesive according to claim 1 or 2, wherein the component (B) is a combination of a (b1) phenylmethylsiloxane unit structure or a diphenylsiloxane unit structure and a (b2) dimethylsiloxane unit structure.
  4. 前記加工が前記ウエハーの裏面研磨である請求項１乃至請求項３のいずれか１項に記載の接着剤。 The adhesive according to any one of claims 1 to 3, wherein the processing is polishing the back surface of the wafer.
  5. 第一基体上に請求項１乃至請求項４のいずれか１項に記載の接着剤を塗布し接着層を形成し、第二基体を接合し、前記第一基体側から加熱する積層体の接合方法。 The adhesive according to any one of claims 1 to 4 is coated on a first substrate to form an adhesive layer, a second substrate is bonded, and bonding of a laminate to be heated from the first substrate side is performed. Method.
  6. 前記第一基体が支持体であり、前記第二基体がウエハーであり、前記ウエハーの回路面が前記第一基体と向き合うものである請求項５に記載の接合方法。 The bonding method according to claim 5, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  7. 前記第一基体がウエハーであり、前記第二基体が支持体であり、前記ウエハーの回路面が前記第二基体と向き合うものである請求項５に記載の接合方法。 6. The bonding method according to claim 5, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
  8. 第一基体上に請求項１乃至請求項３のいずれか１項に記載の接着剤を塗布し接着層を形成し、第二基体を接合し、前記第一基体側から加熱し前記接着剤を硬化させ積層体を形成した後に、前記積層体を加工し、前記第一基体、前記第二基体と前記接着層の間で剥離を生じる剥離方法。 The adhesive according to any one of claims 1 to 3 is coated on a first substrate to form an adhesive layer, a second substrate is joined, and the adhesive is heated by heating from the first substrate side. The peeling method which processes the said laminated body after hardening and forms a laminated body and which peels between the said 1st base | substrate, the said 2nd base | substrate, and the said contact bonding layer.
  9. 第一基体上に請求項４に記載の接着剤を塗布し接着層を形成し、第二基体を接合し、前記第一基体側から加熱し前記接着剤を硬化させ積層体を形成した後に、前記積層体を加工し、前記第一基体、前記第二基体と前記接着層の間で剥離を生じる剥離方法。 The adhesive according to claim 4 is coated on a first substrate to form an adhesive layer, the second substrate is joined, and the adhesive is cured by heating from the first substrate side to form a laminate. A peeling method in which the laminate is processed to cause peeling between the first substrate, the second substrate and the adhesive layer.
  10. 前記第一基体が支持体であり、前記第二基体がウエハーであり、前記ウエハーの回路面が前記第一基体と向き合うものである請求項８に記載の剥離方法。 The peeling method according to claim 8, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  11. 前記第一基体が支持体であり、前記第二基体がウエハーであり、前記ウエハーの回路面が前記第一基体と向き合うものである請求項９に記載の剥離方法。 10. The peeling method according to claim 9, wherein the first substrate is a support, the second substrate is a wafer, and the circuit surface of the wafer faces the first substrate.
  12. 前記第一基体がウエハーであり、前記第二基体が支持体であり、前記ウエハーの回路面が前記第二基体と向き合うものである請求項８に記載の剥離方法。 9. The peeling method according to claim 8, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
  13. 前記第一基体がウエハーであり、前記第二基体が支持体であり、前記ウエハーの回路面が前記第二基体と向き合うものである請求項９に記載の剥離方法。 10. The peeling method according to claim 9, wherein the first substrate is a wafer, the second substrate is a support, and the circuit surface of the wafer faces the second substrate.
  14. 前記加工が前記ウエハーの裏面研磨である請求項８、１０、１２のいずれか１項に記載の剥離方法。 The peeling method according to any one of claims 8, 10 and 12, wherein the processing is polishing the back surface of the wafer.
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